CN115406987B - Method for establishing GC-MS detection analysis conditions of halosulfuron-methyl - Google Patents
Method for establishing GC-MS detection analysis conditions of halosulfuron-methyl Download PDFInfo
- Publication number
- CN115406987B CN115406987B CN202211044321.2A CN202211044321A CN115406987B CN 115406987 B CN115406987 B CN 115406987B CN 202211044321 A CN202211044321 A CN 202211044321A CN 115406987 B CN115406987 B CN 115406987B
- Authority
- CN
- China
- Prior art keywords
- halosulfuron
- methyl
- detection
- temperature
- standard working
- 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.)
- Active
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
-
- 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
- G01N30/16—Injection
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
-
- 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
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
- G01N30/6073—Construction of the column body in open tubular form
- G01N30/6078—Capillaries
-
- 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
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
-
- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
- G01N2030/3076—Control of physical parameters of the fluid carrier of temperature using specially adapted T(t) profile
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
- G01N2030/324—Control of physical parameters of the fluid carrier of pressure or speed speed, flow rate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The method for establishing the GC-MS detection analysis conditions of the halosulfuron-methyl comprises the steps of determining qualitative and quantitative ions in a full-scan mode, detecting the halosulfuron-methyl in an ion monitoring mode, and finally optimizing each parameter to determine the GC-MS detection conditions of the halosulfuron-methyl: the chromatographic column is Agilent capillary column HP-5MS; the temperature of the sample inlet is 290 ℃, the temperature is programmed, the sample is not split, the sample feeding amount is 2 mu L, and the flow rate is 1.2mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; the solvent delay time is 2.0min, the data acquisition mode is an ion monitoring mode, the halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10, and the quantitative ions are m/z 327.10. The halosulfuron-methyl is detected by the method established by the GC-MS detection condition, the linear relation is good, and the minimum detection limit is 0.01mg/L.
Description
Technical Field
The invention belongs to the field of chemical analysis and detection, relates to qualitative and quantitative detection analysis of halosulfuron-methyl, and in particular relates to a method for establishing gas chromatography-mass spectrometry (GC-MS) detection analysis conditions of halosulfuron-methyl.
Background
Halosulfuron-methyl (chemical name: 3- (4, 6-dimethoxy pyrimidine-2-yl) -1- (1-methyl-3-chloro-4-methoxy formyl pyrazole-5-yl) sulfonylurea, formula C 13 H 15 C 1 N 6 O 7 S, molecular weight 434.81, belongs to sulfonylurea herbicides. The herbicide is mainly used for preventing and killing broadleaf weeds and sedge weeds, and has high selectivity to gramineous crops such as corn, rice, wheat, sugarcane and the like. The mechanism of action is that the synthesis of protein is finally destroyed by inhibiting the biosynthesis of branched chain amino acid and the like through inhibiting the acetolactate synthase of plants, and the synthesis of DNA and the division and growth of cells are interfered.
At present, the detection method of halosulfuron-methyl at home and abroad mainly comprises a liquid chromatograph and a liquid chromatograph-mass spectrometer. There has been no report on the measurement of halosulfuron-methyl by gas chromatography-mass spectrometry (GC-MS).
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for establishing gas chromatography-mass spectrometry (GC-MS) detection analysis conditions of halosulfuron-methyl so as to carry out qualitative and quantitative detection analysis on the halosulfuron-methyl by the established GC-MS detection analysis conditions.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for establishing GC-MS detection analysis conditions of halosulfuron-methyl comprises the following steps:
A. preparing a standard working solution: and dissolving a halosulfuron-methyl standard product by using acetone, and preparing a standard working solution to ensure that the mass concentration of the halosulfuron-methyl is 0.01, 0.05, 0.10, 0.50, 1.00, 5.0 and 10.0mg/L.
In the steps, the acetone is utilized to dissolve the halosulfuron-methyl, and then the halosulfuron-methyl standard mother liquor with the mass concentration of 1000.0mg/L is prepared, and then the standard mother liquor is diluted into the standard working solution.
B. Full scan mode detection determines qualitative and quantitative ions: performing full-scan mode detection on acetone, 1mg/L and 10mg/L of halosulfuron-methyl standard working solution for preparing the halosulfuron-methyl standard working solution, and obtaining a total ion chromatogram of a full-scan gas chromatograph-mass spectrum of the halosulfuron-methyl standard solution, wherein m/z is 50-600, so as to further obtain a halosulfuron-methyl full-scan mass chromatogram, and finding 3 characteristic ion fragments with the maximum sensitivity, namely the maximum abundance, on the halosulfuron-methyl full-scan mass chromatogram as qualitative and quantitative ions, namely m/z139.10, 260.10 and 327.10, wherein the quantitative ions are m/z 327.10;
the method for obtaining the halosulfuron-methyl full-scanning mass spectrogram comprises the following steps of: in the total ion chromatogram of the total scavenging phase chromatogram-mass spectrum of the halosulfuron-methyl standard solution, if a new chromatographic peak appears in the standard working solution and the low concentration and the high concentration of the new chromatographic peak are in direct proportion, judging that the new chromatographic peak is the chromatographic peak of halosulfuron-methyl; double-click of chromatographic peaks of halosulfuron-methyl to obtain a halosulfuron-methyl full-sweep mass spectrum.
The GC-MS conditions for the full scan mode mentioned above are: the chromatographic column is Agilent capillary column HP-5MS,30m×0.25mm×0.25um; sample inlet temperature 260 ℃, programming temperature rise: maintaining at 60deg.C for 3.0min, heating to 290 deg.C at 20deg.C/min, and maintaining for 10.0min; carrier gas: helium with a purity of 99.999%; sample introduction is not split, and sample introduction amount is as follows: 1 μL, flow rate 1.0mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; solvent delay time was 2.0min, data acquisition mode: full scan detection, scan m/z50-600.
C. Ion monitoring mode detection: detecting 0.01, 0.05, 0.10, 0.50 and 1.00mg/L of standard working solution on a GC-MS by adopting an ion monitoring mode under the condition that halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10 and quantitative ions are m/z 327.10, wherein other detection conditions of the GC-MS are the same as the full-scanning GC-MS conditions of the step B; if the peak area of the standard working solution of the low-concentration halosulfuron-methyl is too small, the peak cannot be accumulated, and a plurality of small miscellaneous peaks appear, the sensitivity is insufficient, and the instrument parameters need to be adjusted;
D. optimizing gas phase detection conditions, improving sensitivity of halosulfuron-methyl, and determining GC-MS detection analysis conditions of halosulfuron-methyl: and C, under the condition that halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10 and quantitative ions are m/z 327.10, based on the full-scanning GC-MS condition of the step B, detecting 1.00mg/L of standard working solution on the GC-MS by adopting an ion monitoring mode by changing parameters of any one of variable sample injection amount, sample inlet temperature, flow rate, temperature programming or ion source temperature, and determining the GC-MS detection analysis condition of halosulfuron-methyl by comparing whether the peak area of the standard working solution is maximum, the peak outlet time is most suitable and the peak type is symmetrical under different parameter detection conditions.
The GC-MS detection analysis conditions of the halosulfuron-methyl determined in the step D are as follows: the chromatographic column is Agilent capillary column HP-5MS,30m×0.25mm×0.25um; sample inlet temperature 290 ℃, programming temperature rise: maintaining the temperature at 130 ℃ for 1.0min, and heating the temperature to 250 ℃ at 10 ℃/min for 1.0min; heating to 300 ℃ at 10 ℃/min, and keeping for 1.0min; carrier gas: helium with a purity of 99.999%; sample introduction is not split, and sample introduction amount is as follows: 2. Mu.L, flow rate 1.2mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; solvent delay time was 2.0min, data acquisition mode: ion monitoring mode, halosulfuron-methyl monitors ions m/z139.10, 260.10, 327.10, where the quantitative ion is m/z 327.10.
The standard working solution of halosulfuron-methyl is detected by the GC-MS detection analysis condition of halosulfuron-methyl, 0.01, 0.05, 0.10, 0.50 and 1.00mg/L, the standard working curve equation is y= 437997x-4409.8, R is obtained 2 =0.9995, plotted with the mass concentration of halosulfuron-methyl as abscissa and the quantitative ion peak area as ordinate.
According to the invention, GC-MS instrument analysis conditions for detecting the halosulfuron-methyl are established for the first time, the physical and chemical properties of the halosulfuron-methyl are consulted, the parameters of the GC-MS instrument are roughly set, qualitative and quantitative ions of the halosulfuron-methyl are found in a full sweep, and meanwhile, GC-MS detection parameters (sample injection amount, sample inlet temperature, column temperature box temperature and the like) are optimized, so that the separation efficiency and sensitivity are improved. The GC-MS detection and analysis method corresponding to the GC-MS detection and analysis conditions has the characteristics of high sensitivity, good precision, good stability and the like, the lowest detection limit of analysis is 0.01mg/L, and a novel detection method is provided for detecting halosulfuron-methyl.
Drawings
Fig. 1 is a full-sweep mass spectrum of halosulfuron-methyl.
Fig. 2 is a total ion chromatogram of a series of standard halosulfuron-methyl solutions before non-optimized gasconditions in example 1.
FIG. 3 is a total ion chromatogram of an ion monitoring gas chromatograph-mass spectrum of a 1.00mg/L halosulfuron-methyl standard working solution of the present invention.
FIG. 4 is a graph of the relative abundance of ionic fragments for a standard working solution of halosulfuron-methyl of the present invention at 1.00mg/L.
Fig. 5 is a standard working graph of halosulfuron-methyl according to the present invention.
Detailed Description
The following examples are further detailed description of the present invention, but are not limited to the scope of the invention.
The apparatus and reagents used in the examples:
gas chromatograph-mass spectrometer (GC 7890A-MS5975, agilent technologies, inc., usa) equipped with electron bombardment ionization source (EI). Chromatographic column: agilent HP-5MS (30 m. Times.0.25 mm. Times.0.25 um). Halosulfuron-methyl standard (purity 97%) and acetone were chromatographically pure and purchased from Tianjin Dibo chemical Co., ltd.
EXAMPLE 1 confirmation of gas chromatograph-Mass Spectrometry detection conditions for halosulfuron-methyl
1. Preparation of standard working solution
0.1031g (accurate to 0.0001 g) of halosulfuron-methyl standard (purity: 97%) is accurately weighed, placed in a 100mL brown volumetric flask, dissolved with chromatographic acetone and prepared into halosulfuron-methyl standard mother liquor with mass concentration of 1000.0 mg/L. And then, standard mother solutions of the halosulfuron-methyl are respectively prepared into standard working solutions by adopting a gradient dilution method, so that the mass concentration of the halosulfuron-methyl is 0.01, 0.05, 0.10, 0.50, 1.00, 5.0 and 10.0mg/L.
2. Detection in full scan mode to find qualitative and quantitative ions
And (3) performing full scanning (m/z 50-600) on the halosulfuron-methyl standard solution, which is used for preparing the halosulfuron-methyl standard working solution, to obtain a total ion chromatogram of a full scavenging phase chromatogram-mass spectrum of the halosulfuron-methyl standard solution, deducting chromatographic peaks appearing in the acetone, judging that the new chromatographic peaks appear in the standard solution and the low concentration and the high concentration of the new chromatographic peaks are in direct proportion, judging that the new chromatographic peaks are the chromatographic peaks of halosulfuron-methyl, double-clicking the chromatographic peaks to obtain the halosulfuron-methyl full-scanning chromatogram (figure 1), and finding out 3 characteristic ion fragments with the maximum sensitivity, namely the maximum abundance, as qualitative and quantitative ions, namely m/z139.10, 260.10 and 327.10, wherein the quantitative ions are m/z 327.10.
The GC-MS conditions for the full scan were: the chromatographic column is Agilent capillary column HP-5MS,30m×0.25mm×0.25um; sample inlet temperature 260 ℃, programming temperature rise: maintaining at 60deg.C for 3.0min, heating to 290 deg.C at 20deg.C/min, and maintaining for 10.0min; carrier gas: helium with a purity of 99.999%; sample introduction is not split, and sample introduction amount is as follows: 1 μL, flow rate 1.0mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; solvent delay time was 2.0min, data acquisition mode: full scan detection, scan m/z50-600.
3. Ion monitoring mode detection
And (2) under the conditions that halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10 and quantitative ions are m/z 327.10, detecting 0.01, 0.05, 0.10, 0.50 and 1.00mg/L of the standard working solution prepared in the step (1) by adopting an ion monitoring mode on a GC-MS, wherein other detection conditions of the GC-MS are the same as the full-scanning GC-MS conditions of the step (2). Referring to fig. 2, the high concentration standard solutions all peak in retention time and all are linear, while all have halosulfuron-methyl monitoring characteristic ion fragments. However, the standard solution with low concentration has peaks, but the sensitivity is insufficient, and the minimum concentration of 0.01 has a lot of small peak interference because of lower sensitivity, and the integration is inaccurate, so that the instrument parameters need to be adjusted.
4. Optimizing gas phase detection condition and improving sensitivity of halosulfuron-methyl
By optimizing the gas phase conditions, by varying the injection amounts (1 uL,1.5uL and 2 uL), the injection port temperature (260 ℃,270 ℃,280 ℃,290 ℃) and the flow rate (0.8 mL/min,1.0mL/min,1.2 mL/min); and (3) programming the temperature, the ion source temperature (210 ℃,220 ℃,230 ℃) and other parameters to improve the sensitivity of the halosulfuron-methyl.
The method is characterized in that under the conditions that halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10 and quantitative ions are m/z 327.10, the influence of variables on halosulfuron-methyl detection under different parameters (0.8 mL/min,1.0mL/min,1.2mL/min, 220 ℃ C.) and the flow rate (0.5 mL/min,1.2 mL/min) by changing the sample injection amount (1 uL,1.5uL and 2 uL), the sample injection port temperature (240 ℃,260 ℃ C., 290 ℃) and the temperature of the sample injection port, and the temperature of the standard working solution prepared in the step (1) is detected by adopting an ion monitoring mode on GC-MS, the effect of the variable on halosulfuron-methyl detection under different parameters (210 ℃,220 ℃ C., 230 ℃ C.) is considered by comparing the peak area, the peak outlet time and the peak type (the peak area is as good as possible) of the standard working solution under different detection parameter conditions, so as to determine the GC-MS detection conditions of halosulfuron-methyl can be detected, and the results of the table 1-5 below are seen.
TABLE 1 influence of sample injection amount on halosulfuron-methyl detection
| Sample injection amount (uL) | Peak area | Peak time | Peak type |
| 1 | 210461 | 13.983 | Symmetrical with each other |
| 1.5 | 32065 | 13.983 | Symmetrical with each other |
| 2.0 | 412861 | 13.983 | Symmetrical with each other |
The choice of the sample injection amount needs to consider chromatographic columns and weighing tubes used by the instrument, and the overload of the column is easily caused by the excessive sample injection amount. According to the method, different sample injection amounts are reasonably set according to the selected chromatographic column and the selected type of the tube, and as can be seen from Table 1, the change of the sample injection amount has little influence on the chromatographic peak type and the peak outlet time, but has great influence on the response peak area, and the peak area is maximum when the sample injection amount is 2.0uL, and the sensitivity is the best, so that the sample injection amount is determined to be 2.0uL as a detection condition.
TABLE 2 influence of sample inlet temperature on halosulfuron-methyl detection
| Sample inlet temperature (DEG C) | Peak area | Peak time | Peak type |
| 240 | 410319 | 13.983 | Symmetrical with each other |
| 260 | 410496 | 13.983 | Symmetrical with each other |
| 280 | 411983 | 13.983 | Symmetrical with each other |
| 290 | 412861 | 13.983 | Symmetrical with each other |
The requirement of the temperature of the sample inlet is that the components to be tested can be vaporized in the moment without diversion, but the components to be tested cannot be decomposed. As can be seen from Table 2, the variation in the temperature of the sample inlet has little effect on the chromatographic peak pattern and the peak-out time, and also has little effect on the peak area of the response, so that the maximum temperature of 290℃is determined as the detection condition in order to ensure that the sample can be completely gasified.
TABLE 3 influence of gas flow Rate on halosulfuron-methyl detection
In actual detection analysis, the helium flow rate is required to ensure the complete separation of the to-be-detected object and ensure that the peak area and the peak shape meet the detection requirements, and the shorter the analysis time is, the better the analysis time is. As can be seen from Table 3, when the flow rate was 1.2mL/min, the peak area was maximum, the peak shape, the degree of separation and the reproducibility were all good, and the sample injection time was the shortest, so that the flow rate of the mobile phase was determined to be 1.2mL/min as the detection condition.
TABLE 4 influence of temperature programming on halosulfuron-methyl detection
The temperature rise program is determined by changing the influence of the furnace temperature initial temperature and different temperature rise rates to the peak type, the peak area and the peak outlet time of the halosulfuron-methyl. As is clear from table 4, the change in temperature programming has little influence on the chromatographic peak pattern and peak area, but has a great influence on the peak emission time, and the peak area is the largest and the peak emission time is the shortest when the temperature programming of method 3 is applied, so that the temperature programming is determined as the detection condition of method 3.
TABLE 5 influence of ion Source temperature on halosulfuron-methyl detection
| Ion Source temperature (. Degree. C.) | Peak area | Peak time | Peak type |
| 210 | 409912 | 13.983 | Symmetrical with each other |
| 220 | 409938 | 13.983 | Symmetrical with each other |
| 230 | 412861 | 13.983 | Symmetrical with each other |
As is clear from Table 5, the ion source temperature was determined to be the detection condition because the influence of the change in the ion source temperature on the chromatographic peak pattern, the peak-out time and the peak area was not so great, but the peak area was relatively maximum at 230℃and the sensitivity was the best.
On the basis of the analysis, the GC-MS conditions for detecting and analyzing halosulfuron-methyl are determined as follows: the chromatographic column is Agilent capillary column HP-5MS,30m×0.25mm×0.25um; sample inlet temperature 290 ℃, programming temperature rise: maintaining the temperature at 130 ℃ for 1.0min, and heating the temperature to 250 ℃ at 10 ℃/min for 1.0min; heating to 300 ℃ at 10 ℃/min, and keeping for 1.0min; carrier gas: helium with a purity of 99.999%; sample introduction is not split, and sample introduction amount is as follows: 2. Mu.L, flow rate 1.2mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; solvent delay time was 2.0min, data acquisition mode: ion monitoring mode, halosulfuron-methyl monitors ions m/z139.10, 260.10, 327.10, where the quantitative ion is m/z 327.10.
5. Qualitative and quantitative analysis
Qualitative analysis: the halosulfuron-methyl standard working solution was tested under the GC-MS conditions identified above at 0.01, 0.05, 0.10, 0.50, 1.00mg/L. The results show that the peak time of halosulfuron-methyl in the total ion chromatograms of the gas chromatography-mass spectrometry of the halosulfuron-methyl standard working solutions with different gradient concentrations are basically consistent, and fig. 3 shows the total ion chromatograms of the ion monitoring gas chromatography-mass spectrometry of the halosulfuron-methyl standard working solution with the concentration of 1.00mg/L, and the halosulfuron-methyl standard solution is known to be reserved in 13.983 minutes. The ion fragment relative abundance value patterns of the halosulfuron-methyl standard working solution with different gradient concentrations are the same, and fig. 4 shows the ion fragment relative abundance value patterns of the halosulfuron-methyl standard working solution with the concentration of 1.00mg/L, and the monitoring ions are m/z139.10, 260.10 and 327.10.
Quantitative analysis: the method is carried out by adopting a gas chromatography-mass spectrometry combined external standard method. The standard working solutions of halosulfuron-methyl prepared in the previous steps of 0.01, 0.05, 0.10, 0.50 and 1.00mg/L are measured under the above-determined GC-MS detection conditions, and each mass concentration is sampled 3 times, and 5 concentrations are added. And (3) carrying out progressive regression by taking the mass concentration (X, mg/L) of halosulfuron-methyl as an abscissa and the quantitative ion peak area (Y) as an ordinate, and calculating a correlation coefficient (r). The results are shown in Table 6 and FIG. 5.
TABLE 6 Standard working curves for halosulfuron-methyl
As can be seen from Table 6 and FIG. 5, the standard working curve equation of halosulfuron-methyl is y= 437997x-4409.8, R 2 =0.9995, the linearity was good. The minimum limit of detection for analysis as described above was 0.01mg/L.
EXAMPLE 2 examination of the linearity, precision and accuracy of the gas chromatography-Mass Spectrometry detection method of halosulfuron-methyl
1. Linear relationship investigation
And respectively transferring a proper amount of stock solution of the standard working solution of halosulfuron-methyl, and preparing a series of reference standard solutions with mass concentrations of halosulfuron-methyl of 0.01, 0.05, 0.10, 0.50 and 1.00mg/L by using acetone. Placing the sample into a sample injection vial, placing the sample into an automatic sampler, running an automatic sample injection program, injecting the sample into a GC-MS analyzer, and detecting and analyzing conditions, wherein the conditions are determined in the embodiment 1, and injecting the sample into each mass concentration 3 times for 5 points. Regression analysis was performed with the mass concentration (X, mg/L) of the target compound as the abscissa and the quantitative ion peak area (Y) as the ordinate, and the correlation coefficient (r) was calculated. The results are shown in Table 6 and FIG. 5. As can be seen from table 6 and fig. 5, the peak area of halosulfuron-methyl in a certain linear range has a good linear relationship with concentration, and the correlation coefficient is 0.9995.
The detection Limit (LOD) is the lowest concentration of an analysis object which can be detected by an analysis method under the same condition in the sample measurement process, and the minimum detection limit of halosulfuron-methyl which is analyzed under the GC-MS detection condition determined by the invention is 0.01mg/L.
2. Analytical method precision determination
Taking the prepared standard solution (1 mg/L) of halosulfuron-methyl, and sub-packaging into 5 sample injection bottles. A certain amount of 75% halosulfuron-methyl water dispersible granule is weighed, placed in a volumetric flask of 100mL, dissolved and diluted to a scale by chromatographic acetone, and shaken uniformly to form a sample solution. 5 parts of parallel samples are weighed by the same method to form 5 parts of sample solution, the sample solution is placed into a sample injection small bottle, then the sample solution is placed into an automatic sampler, the standard solution is placed first, then the automatic sample injection program is operated in sequence of the sample solution, the sample solution is injected into a GC-MS analyzer, the sample is injected and detected according to the GC-MS detection analysis conditions determined in example 1 (the mass fraction of halosulfuron-methyl in the sample is calculated as the prior conventional technology), and the measurement precision of the sample is checked, and the result is shown in Table 7. The experimental results show that: the standard deviation of the content of 5 parts of halosulfuron-methyl pesticide sample is 0.02, the variation coefficient is 2.48%, and the sample measurement method has good precision.
TABLE 7 precision test results of halosulfuron-methyl GC-MS method
3. Accuracy determination of analytical methods
In order to examine the accuracy of the analysis method, a labeled recovery experiment was performed on the sample. A certain amount of halosulfuron-methyl Long Biaoyang was added to a water-dispersible granule sample of 75% halosulfuron-methyl of known content, and the content was measured by GC-MS detection analysis method determined in example 1, and the labeled recovery was calculated (recovery was calculated as in the conventional art). The results are shown in Table 8, and the results show that the average recovery rates of halosulfuron-methyl are 103% respectively. The method has higher accuracy and can meet the quantitative analysis requirement.
Table 8 accuracy test results of halosulfuron-methyl method
From the above, the GC-MS detection analysis method corresponding to the GC-MS detection analysis conditions established by the invention has the advantages of higher accuracy and precision, good linear relation, simplicity, convenience, rapidness and good accurate separation effect, and is a feasible analysis method.
The above embodiments are provided to illustrate the technical solution of the present invention, not to limit the technical solution, and it is intended to enable those skilled in the art to understand the content of the present invention and implement the same, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (8)
1. The method for establishing the GC-MS detection analysis conditions of halosulfuron-methyl is characterized by comprising the following steps:
A. preparing a standard working solution: dissolving a halosulfuron-methyl standard product by using acetone, and preparing a standard working solution to ensure that the mass concentration of the halosulfuron-methyl is 0.01, 0.05, 0.10, 0.50, 1.00, 5.0 and 10.0mg/L;
B. full scan mode detection determines qualitative and quantitative ions: performing full-scan mode detection on acetone, 1mg/L and 10mg/L of halosulfuron-methyl standard working solution for preparing the halosulfuron-methyl standard working solution, and obtaining a total ion chromatogram of a full-scan gas chromatograph-mass spectrum of the halosulfuron-methyl standard solution, wherein m/z is 50-600, so as to further obtain a halosulfuron-methyl full-scan mass chromatogram, and finding 3 characteristic ion fragments with the maximum sensitivity, namely the maximum abundance, on the halosulfuron-methyl full-scan mass chromatogram as qualitative and quantitative ions, namely m/z139.10, 260.10 and 327.10, wherein the quantitative ions are m/z 327.10;
C. ion monitoring mode detection: detecting 0.01, 0.05, 0.10, 0.50 and 1.00mg/L of standard working solution on a GC-MS by adopting an ion monitoring mode under the condition that halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10 and quantitative ions are m/z 327.10, wherein other detection conditions of the GC-MS are the same as the full-scanning GC-MS conditions of the step B; if a plurality of small impurity peaks appear in the low-concentration standard working solution, the peak area is too small and the peaks cannot be accumulated, the sensitivity is insufficient, and the instrument parameters need to be adjusted;
D. optimizing gas phase detection conditions, improving sensitivity of halosulfuron-methyl, and determining GC-MS detection analysis conditions of halosulfuron-methyl: and C, under the condition that halosulfuron-methyl monitors ions m/z139.10, 260.10 and 327.10 and quantitative ions are m/z 327.10, based on the full-scanning GC-MS condition of the step B, detecting 1.00mg/L of standard working solution on the GC-MS by adopting an ion monitoring mode through changing parameters of any one of variable sample injection amount, sample inlet temperature, flow rate, temperature programming or ion source temperature, and determining the GC-MS detection analysis condition of halosulfuron-methyl by comparing whether the peak area of the standard working solution is maximum, the peak outlet time is proper and the peak type is symmetrical under the variable detection conditions of different parameters.
2. The method for establishing GC-MS detection and analysis conditions of halosulfuron-methyl according to claim 1, wherein the GC-MS detection and analysis conditions of halosulfuron-methyl determined in the step D are as follows: the chromatographic column is Agilent capillary column HP-5MS,30m×0.25mm×0.25um; sample inlet temperature 290 ℃, programming temperature rise: maintaining the temperature at 130 ℃ for 1.0min, and heating the temperature to 250 ℃ at 10 ℃/min for 1.0min; heating to 300 ℃ at 10 ℃/min, and keeping for 1.0min; carrier gas: helium with a purity of 99.999%; sample introduction is not split, and sample introduction amount is as follows: 2. Mu.L, flow rate 1.2mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; solvent delay time was 2.0min, data acquisition mode: ion monitoring mode, halosulfuron-methyl monitors ions m/z139.10, 260.10, 327.10, where the quantitative ion is m/z 327.10.
3. The method for establishing GC-MS detection analysis conditions of halosulfuron-methyl as described in claim 2, which comprisesCharacterized in that the standard working solution of halosulfuron-methyl is detected by GC-MS detection analysis conditions of the halosulfuron-methyl, the standard working curve equation is y= 437997x-4409.8, R is obtained, the standard working solution is 0.01, 0.05, 0.10, 0.50 and 1.00mg/L 2 ＝0.9995。
4. The method for establishing GC-MS detection analysis conditions of halosulfuron-methyl according to claim 3, wherein the standard working curve equation is drawn by taking the mass concentration of halosulfuron-methyl as an abscissa and the quantitative ion peak area as an ordinate.
5. The method for establishing GC-MS detection analysis conditions of halosulfuron-methyl as defined in claim 2, wherein the minimum detection limit of the GC-MS detection analysis conditions of halosulfuron-methyl is 0.01mg/L.
6. The method for establishing GC-MS detection and analysis conditions of halosulfuron-methyl according to claim 1, wherein the GC-MS conditions of the full scan mode in step B are: the chromatographic column is Agilent capillary column HP-5MS,30m×0.25mm×0.25um; sample inlet temperature 260 ℃, programming temperature rise: maintaining at 60deg.C for 3.0min, heating to 290 deg.C at 20deg.C/min, and maintaining for 10.0min; carrier gas: helium with a purity of 99.999%; sample introduction is not split, and sample introduction amount is as follows: 1 μL, flow rate 1.0mL/min; quadrupole temperature 150 ℃, ion source temperature 230 ℃, mass spectrum transmission line temperature 280 ℃; solvent delay time was 2.0min, data acquisition mode: full scan detection, scan m/z50-600.
7. The method for establishing the GC-MS detection and analysis conditions of halosulfuron-methyl as set forth in claim 1, wherein the step B comprises the steps of: in the total ion chromatogram of the total scavenging phase chromatogram-mass spectrum of the halosulfuron-methyl standard solution, if a new chromatographic peak appears in the standard working solution and the low concentration and the high concentration of the new chromatographic peak are in direct proportion, judging that the new chromatographic peak is the chromatographic peak of halosulfuron-methyl; double-click of chromatographic peaks of halosulfuron-methyl to obtain a halosulfuron-methyl full-sweep mass spectrum.
8. The method for establishing the GC-MS detection analysis conditions of the halosulfuron-methyl according to claim 1, wherein in the step A, acetone is utilized to dissolve the halosulfuron-methyl, then standard mother liquor of the halosulfuron-methyl with the mass concentration of 1000.0mg/L is prepared, and then the standard mother liquor is diluted into a standard working solution according to a gradient dilution method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211044321.2A CN115406987B (en) | 2022-08-30 | 2022-08-30 | Method for establishing GC-MS detection analysis conditions of halosulfuron-methyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211044321.2A CN115406987B (en) | 2022-08-30 | 2022-08-30 | Method for establishing GC-MS detection analysis conditions of halosulfuron-methyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115406987A CN115406987A (en) | 2022-11-29 |
| CN115406987B true CN115406987B (en) | 2023-08-08 |
Family
ID=84162505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211044321.2A Active CN115406987B (en) | 2022-08-30 | 2022-08-30 | Method for establishing GC-MS detection analysis conditions of halosulfuron-methyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115406987B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110470768A (en) * | 2019-08-27 | 2019-11-19 | 谱尼测试集团吉林有限公司 | Pyrazosulfuron in a kind of measurement water quality, Hostathion, butachlor residue amount method |
| WO2020232970A1 (en) * | 2019-05-17 | 2020-11-26 | 江南大学 | Method for determining short chain fatty acid content in intestinal contents or excrement |
-
2022
- 2022-08-30 CN CN202211044321.2A patent/CN115406987B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020232970A1 (en) * | 2019-05-17 | 2020-11-26 | 江南大学 | Method for determining short chain fatty acid content in intestinal contents or excrement |
| CN110470768A (en) * | 2019-08-27 | 2019-11-19 | 谱尼测试集团吉林有限公司 | Pyrazosulfuron in a kind of measurement water quality, Hostathion, butachlor residue amount method |
Non-Patent Citations (1)
| Title |
|---|
| 高效液相色谱-串联质谱检测水稻中氯吡嘧磺隆残留量;张爱娟;马新刚;梁林;冯义志;潘金菊;齐晓雪;韩济峰;左伯军;;农药科学与管理(第01期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115406987A (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| De Vos et al. | Untargeted large-scale plant metabolomics using liquid chromatography coupled to mass spectrometry | |
| CN108918711B (en) | Detection method of polyphenol compounds in tobacco leaves | |
| CN111735870A (en) | Correction method and correction device for online real-time analysis of mass spectrum | |
| CN110133156A (en) | The analysis method of super more target flavor components in a kind of high throughput assay tobacco juice for electronic smoke | |
| CN112730706A (en) | Method for detecting biological small molecule marker by liquid chromatography-tandem mass spectrometry | |
| CN111398487A (en) | Application method of retention index in gas chromatography-tandem mass spectrometry analysis of tobacco flavor components | |
| CN115406987B (en) | Method for establishing GC-MS detection analysis conditions of halosulfuron-methyl | |
| CN110850002B (en) | Method for quantifying honey MRJP2 in liquid chromatography tandem mass spectrometry | |
| CN108956812B (en) | Method for detecting water-soluble organic chloride pesticide residue in soil | |
| CN108152410B (en) | method for rapidly detecting chiral triadimenol in grains | |
| CN109212076B (en) | Method for detecting oxyfluorfen in water by using HPLC-MS/MS method | |
| CN115541789A (en) | Method for measuring nicotine salt content in tobacco and tobacco products | |
| CN113295794B (en) | Rapid screening method for content of multiple types of nonvolatile risk substances in white spirit | |
| CN113109471B (en) | LCMSMS (liquid crystal display module medium) method for rapidly and simultaneously detecting chlorothalonil and metabolites thereof in vegetables and fruits | |
| CN111595979A (en) | Ultra-high performance liquid chromatography-tandem mass spectrometry method for simultaneously determining content of metamifop and metabolite thereof | |
| CN112129873B (en) | Method for detecting cyanophos pesticide residue in soil | |
| CN113203815A (en) | Method for detecting triafamone and metabolites thereof in brown rice, rice hulls and straws based on UPLC-MSMS | |
| CN111024872B (en) | Method for rapidly detecting 3-methylthio propanol in sesame-flavor liquor | |
| CN114217002A (en) | Method for detecting content of chamomile azulene and sabinene in blumea oil | |
| CN111398486A (en) | Method for rapidly determining acquisition time window in gas chromatography-tandem mass spectrometry dynamic multi-reaction monitoring mode analysis method | |
| CN113030320A (en) | Separation and identification method and application of low molecular weight aldehyde | |
| Sun et al. | Highly sensitive and specific detection of histamine via the formation of a self-assembled magic number cluster with thymine by mass spectrometry | |
| CN109324139A (en) | Ribosylzeatin liquid-liquid extraction-liquid chromatography-tandem mass spectrometry measuring method in a kind of tobacco leaf | |
| CN111505182A (en) | Method for measuring dimethyl sulfate in medicine by derivatization gas chromatography-mass spectrometry | |
| CN111272897B (en) | Detection method of 2-amino-4,6-dihydroxypyrimidine and 4-amino-2,6-dihydroxypyrimidine in pemetrexed acid |
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 |