CN103575798B - Liquid Chromatography-Tandem Mass Spectrometry measures the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton - Google Patents
Liquid Chromatography-Tandem Mass Spectrometry measures the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton Download PDFInfo
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Abstract
The present invention relates to a kind of method that Liquid Chromatography-Tandem Mass Spectrometry measures ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, method is as follows: 1) sample preparation; 2) measure; 3) judge: with mass concentration X as horizontal ordinate, peak area Y is ordinate, draws 5 standard working curves, carries out quantitatively with standard working curve to sample, and the response of sample solution Chinese traditional medicine should in the range of linearity of instrument detection; Method of the present invention is easy, quick, accurate, and all technical meets the requirement of domestic and international regulation, can be used for the quantitative detection of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid in cotton samples, Thidiazuron and diuron.
Description
Technical field
The present invention relates to a kind of method measuring cotton Pesticide Residues, particularly relate to a kind of method that Liquid Chromatography-Tandem Mass Spectrometry measures ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton.
Background technology
Along with improving constantly of living standard, the consumption idea of people is also constantly being improved.What dress not only will be worn is warm, also beautiful, more wants safety and health simultaneously.The different phase of Cotton Production must use different agricultural chemicals, with pre-preventing disease and pest and weed growth, if do not add control, will affect the seed output and quality of cotton fiber.Although most of agricultural chemicals is removed in processing process in textile, but still have part residues of pesticides in textile, be absorbed by the body with these agricultural chemicals in the process of contact human skin, toxic and side effect can be produced to human body, severe one can bring out cancer, and the residues of pesticides in addition in textile industry in cotton can polluted water and soil.
Ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron can impel cotton leaf to come off, and are conducive to mechanical harvesting, and without dead leaf fragment on cotton-wool, significantly improve cotton quality.
Current bibliographical information high effective liquid chromatography for measuring (HPLC) measures Thidiazuron in cotton, as Sun Jin etc., and defoliant Thidiazuron detection method research in cotton. standard science, 2010,9,22 ~ 25; Flat vertical phoenix etc., ultra-performance liquid chromatography measures diuron in sugarcane and soil and remains. Journal of Analytical Science, 201127(2) and 235 ~ 237; Guo Yongze etc., Thidiazuron and isomeride thereof be determination of residual amount method [J] in cottonseed and soil. agricultural chemicals, 2005,44(3): 123 ~ 124, the mensuration lower bound of 3 kinds of above-mentioned methods is 0.01 ~ 0.5mg/kg.Guo Yongze etc., the assay method [J] of diuron and metabolic product residual quantity thereof in cottonseed. Tianjin agricultural sciences, 2010,16(3): 69 ~ 71. adopt gas chromatography-nitrogen phosphorous detector (GC-NPD) to determine the residual quantity of diuron in cottonseed.Detecting of method is limited to 0.05mg/kg, and the recovery is 80.56% ~ 94.14%.Have no the bibliographical information of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid residual quantity in cotton and textile.
In food, ethephon (CEPHA)，2-(chloroethyl) phosphonic acid residues detection generally adopts ethephon (CEPHA)，2-(chloroethyl) phosphonic acid to be heated in alkaline aqueous solution and can be rapidly decomposed into the characteristic of ethene, add appropriate high alkali liquid in the sample to which, and at 70 DEG C heated at constant temperature, Headspace Gas Chromatography, as Kong Xianghong, Deng, the residual quantity of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid in headspace gas chromatography Fast Measurement SDS in broiler chickens, assay office, 2010,29(4) 18 ~ 21, the method measures lower bound 0.01mg/kg.Along with reaching its maturity of Liquid Chromatography-Tandem Mass Spectrometry technical development, the method is more and more applied to be measured and confirms textile and Pesticide Residues, above-mentioned method adopts liquid chromatography tandem mass spectrometry to measure ethephon (CEPHA)，2-(chloroethyl) phosphonic acid in fruit, but non-Simultaneously test Thidiazuron and diuron, have employed 20mM acetate buffer solution in mobile phase simultaneously, solution easily produces flocculent deposit blocking mobile phase filter, and method poor reproducibility.Have not yet to see the report of the liquid chromatography-mass spectrography/mass spectroscopy once simultaneously detecting ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron in cotton and plant sample.
Summary of the invention
In order to solve above-mentioned technical matters, the object of this invention is to provide a kind of method that Liquid Chromatography-Tandem Mass Spectrometry measures ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, the method is easy, stable, measuring lower bound is that ethephon (CEPHA)，2-(chloroethyl) phosphonic acid and diuron are 40 μ g/kg, Thidiazuron is 4 μ g/kg, the recovery and precision all meet retention analysis requirement, and meet the requirement of domestic and international regulations to cotton Pesticide Residues completely, and the supervision that can be imported cotton flower residues of pesticides provides technical support.
In order to realize above-mentioned object, present invention employs following technical scheme:
Liquid Chromatography-Tandem Mass Spectrometry measures the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, and the method comprises the following steps:
1) sample preparation
Take homogeneous sample 1g, be accurate to 0.01g, be placed in 50mL tool plug centrifuge tube, add the methanol-water of 20mLpH=8, the volume ratio of methanol-water is 6:4,20min is extracted in jolting, with the centrifugal 5min of 6000r/min, get supernatant and cross the organic filter membrane of 0.22mm, for liquid chromatography tandem mass spectroscopy;
2) measure
Sample introduction under the Liquid Chromatography-Tandem Mass Spectrometry condition that standard working solution and sample solution set at table 1 and table 2:
The mass spectrometry parameters of table 1 ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals
Wherein * represents quota ion;
2. the instrument condition parameter of Liquid Chromatography-Tandem Mass Spectrometry
Liquid chromatography:
| Chromatographic column | Agilent ZORBAX Eclipse XDB-C 8Chromatographic column, 150mm × 4.6mm, 5 μm |
| Mobile phase | Methanol-water, the volume ratio of methanol-water is 6:4 |
| Flow velocity | 0.4mL/min |
| Sample size | 20μL |
| Column temperature | Room temperature |
Mass Spectrometry Conditions:
| Ion gun | Electric spray ion source |
| Scan mode | Negative ion scans |
| Monitoring mode | Multiple-reaction monitoring |
| Electron spray voltage (IS) | -4500V |
| Atomization gas pressure (GS1) | High pure nitrogen, 42psi |
| Gas curtain atmospheric pressure (CUR) | High pure nitrogen, 27psi |
| Assisted gas flow velocity (GS2) | High pure nitrogen, 45psi |
| Ion source temperature (TEM) | High pure nitrogen, 525 DEG C |
| Collision gas (CAD) | High pure nitrogen, 5 |
The maximum allowable offset of relative abundance of ions during qualitative confirmation:
Relative ion abundance > 50%, relative deviation ± 20% of permission
Relative ion abundance > 20% ~ 50%, relative deviation ± 25% of permission
Relative ion abundance > 10% ~ 20%, relative deviation ± 30% of permission
Relative ion abundance≤10%, relative deviation ± 50% of permission;
3) judge
With mass concentration X for horizontal ordinate, peak area Y is ordinate, draws 5 standard working curves, carries out quantitatively with standard working curve to sample, and the response of sample solution Chinese traditional medicine should in the range of linearity of instrument detection; Under above-mentioned chromatographic condition, corresponding measured object whether is there is in judgement sample, the following condition of demand fulfillment: the mass chromatography peak retention time occurred in sample solution is consistent with hybrid standard working fluid, permissible variation is less than ± and 2.5%, medicine corresponding to this chromatographic peak is consistent in the relative abundance of the relative abundance of the mass spectrometry ion mixed-matrix standard working solution suitable with concentration, relative abundance deviation is no more than above-mentioned regulation, then can determine containing this medicine.
The present invention, owing to have employed above-mentioned technical scheme, extracts 3 plant growth regulators in cotton with methanol-water jolting, and Liquid Chromatography-Tandem Mass Spectrometry instrument measures, and negative ion scan mode, multiple-reaction monitoring is often planted each two pairs of ions of agricultural chemicals and carried out qualitative and quantitative analysis.Ethephon (CEPHA)，2-(chloroethyl) phosphonic acid and diuron are at 0 ~ 10 μ g/L; Thidiazuron is related coefficient (r) all about 0.99 within the scope of 1 ~ 1 μ g/L.Respectively with each medicine LOQ, 2LOQ and 4LOQ concentration level recovery testu, recovery scope is 77.5% ~ 109%; Relative standard deviation 5.7% ~ 11.4%; Method detect and track (LOQ) ethephon (CEPHA)，2-(chloroethyl) phosphonic acid and diuron are 40 μ g/kg, and Thidiazuron is 4 μ g/kg.This method is easy, quick, accurate, and all technical meets the requirement of domestic and international regulation, can be used for the quantitative detection of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid in cotton samples, Thidiazuron and diuron.
Accompanying drawing explanation
Fig. 1 is the selectivity ion flow graph of blank cotton samples.
Fig. 2 is the selectivity ion flow graph of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution.
Fig. 3 is the selectivity ion flow graph that blank cotton samples adds ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution (40/4 μ g/kg).
Embodiment
1, sample preparation
Take homogeneous sample 1g (being accurate to 0.01g), be placed in 50mL tool plug centrifuge tube, add the methanol-water (6:4 of 20mLpH=8, V/V), 20min is extracted in jolting, with the centrifugal 5min of 6000r/min, get supernatant and cross the organic filter membrane of 0.22mm, for liquid chromatography tandem mass spectroscopy.
2, measure
Sample introduction under the Liquid Chromatography-Tandem Mass Spectrometry condition that standard working solution and sample solution set at table 1 and table 2, with mass concentration X(μ g/kg) for horizontal ordinate, peak area Y is ordinate, draw 5 standard working curves, carry out quantitatively with standard working curve to sample, the response of sample solution Chinese traditional medicine should in the range of linearity of instrument detection.Under above-mentioned chromatographic condition, corresponding measured object whether is there is in judgement sample, the following condition of demand fulfillment: the mass chromatography peak retention time occurred in sample solution is consistent with hybrid standard working fluid, permissible variation is less than ± and 2.5%, the relative abundance of the mixed-matrix standard working solution that the relative abundance of the mass spectrometry ion in table 2 of the medicine corresponding to this chromatographic peak is suitable with concentration is consistent, relative abundance deviation is no more than the regulation of table 2, then can determine containing this medicine.
Table 1 is parent ion, the mass spectrometry parameters such as daughter ion and collision energy of various kinds of drug.Under the Liquid Chromatography-Tandem Mass Spectrometry condition that table 2 sets, the recovery scope of blank cotton samples interpolation recovery experiment and precision are in table 3, and the selectivity ion flow graph of blank cotton samples, ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution, blank cotton samples interpolation ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution is shown in Fig. 1 ~ Fig. 3.
The mass spectrometry parameters of table 1 ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals
* quota ion is represented
The instrument condition parameter of table 2 Liquid Chromatography-Tandem Mass Spectrometry
Ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals TIANZHU XINGNAO Capsul and precision (n=6) in table 3 cotton
Claims (1)
1. Liquid Chromatography-Tandem Mass Spectrometry measures the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, it is characterized in that the method comprises the following steps:
1) sample preparation
Take homogeneous sample 1g, be accurate to 0.01g, be placed in 50mL tool plug centrifuge tube, add the methanol-water of 20mLpH=8, the volume ratio of methanol-water is 6:4, and 20min is extracted in jolting, with the centrifugal 5min of 6000r/min, get supernatant and cross 0.22 μm of organic filter membrane, for liquid chromatography tandem mass spectroscopy;
2) measure
Standard working solution and sample solution sample introduction under the Liquid Chromatography-Tandem Mass Spectrometry condition of following setting:
1. the mass spectrometry parameters of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals
Ethephon (CEPHA)，2-(chloroethyl) phosphonic acid: with reference to retention time 6.4min, monitoring ion 142.7/107.0*, 142.7/79.3m/z, remove a bunch voltage-40V, collision energy-17eV ,-25eV;
Thidiazuron: with reference to retention time 9.1min, monitoring ion 219.2/100.0*, 219.2/70.9m/z, remove a bunch voltage-55V, collision energy-17eV ,-46eV;
Diuron is with reference to retention time 17.0min, and monitoring ion 231.1/186.0*, 231.1/149.8m/z, remove a bunch voltage-90V, collision energy-25eV ,-34eV;
Wherein * represents quota ion;
2. the instrument condition parameter of Liquid Chromatography-Tandem Mass Spectrometry
Liquid chromatography:
Chromatographic column: AgilentZORBAXEclipseXDB-C
8chromatographic column, 150mm × 4.6mm, 5 μm;
Mobile phase: methanol-water, the volume ratio of methanol-water is 6:4;
Flow velocity: 0.4mL/min;
Sample size: 20 μ L;
Column temperature: room temperature;
Mass Spectrometry Conditions:
Ion gun: electric spray ion source
Scan mode: negative ion scans
Monitoring mode: multiple-reaction monitoring
Electron spray voltage (IS) :-4500V
Atomization gas pressure (GS1): high pure nitrogen, 42psi;
Gas curtain atmospheric pressure (CUR): high pure nitrogen, 27psi
Assisted gas flow velocity (GS2): high pure nitrogen, 45psi;
Ion source temperature (TEM): high pure nitrogen, 525 ° of C
Collision gas (CAD): high pure nitrogen, 99.999%
The maximum allowable offset of relative abundance of ions during qualitative confirmation:
Relative ion abundance >50%, relative deviation ± 20% of permission
20% < relative ion abundance≤50%, relative deviation ± 25% of permission
10% < relative ion abundance≤20%, relative deviation ± 30% of permission
Relative ion abundance≤10%, relative deviation ± 50% of permission;
3) judge
With mass concentration X for horizontal ordinate, peak area Y is ordinate, draws 5 standard working curves, carries out quantitatively with standard working curve to sample, and the response of sample solution Chinese traditional medicine should in the range of linearity of instrument detection; Under above-mentioned chromatographic condition, corresponding measured object whether is there is in judgement sample, the following condition of demand fulfillment: the mass chromatography peak retention time occurred in sample solution is consistent with hybrid standard working fluid, permissible variation is less than ± and 2.5%, medicine corresponding to this chromatographic peak is consistent in the relative abundance of the relative abundance of the mass spectrometry ion mixed-matrix standard working solution suitable with concentration, relative abundance deviation is no more than above-mentioned regulation, then can determine containing this medicine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103969363A (en) * | 2014-04-09 | 2014-08-06 | 温州市质量技术监督检测院 | Detection method for plant growth regulator residues in fruits |
| CN105203652A (en) * | 2015-08-21 | 2015-12-30 | 河南省农业科学院农业质量标准与检测技术研究所 | Method for detecting regulating-agent thidiazuron residues and regulating-agent diuron residues |
| CN108760949B (en) * | 2018-04-20 | 2020-12-08 | 公安部物证鉴定中心 | Method for detecting ethephon serving as plant growth regulator in biological fluid |
| CN108828101B (en) * | 2018-08-08 | 2021-05-07 | 广西科技师范学院 | Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline |
| CN110470759A (en) * | 2019-08-16 | 2019-11-19 | 谱尼测试集团吉林有限公司 | A kind of method of ethephon (CEPHA),2-(chloroethyl) phosphonic acid residual quantity in measurement fruits and vegetables |
| CN115452999A (en) * | 2022-09-28 | 2022-12-09 | 普研（上海）标准技术服务有限公司 | Method for measuring residual quantity of diuron in beef |
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