CN108918709B - Screening and quantitative detection method for common herbicides in blood and application - Google Patents
Screening and quantitative detection method for common herbicides in blood and application Download PDFInfo
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Abstract
The invention relates to a screening and quantitative detection method of common herbicides in blood, which is characterized by comprising the following steps: pretreating a blood sample by a protein precipitation method, and detecting the herbicide in the blood sample by a liquid chromatography/high-resolution mass spectrometry combined analysis method. The method can remove protein precipitates interfering with measurement after the blood sample is pretreated by a protein precipitation method, retain the herbicide to be measured in the blood sample, and can quickly, simply and conveniently extract various herbicides in the blood by matching with a liquid chromatography/high-resolution mass spectrometry combined analysis method. The method can be used for analyzing the types and the contents of the herbicides in the blood samples in the process of determining the cause of death due to poisoning by a forensic doctor.
Description
Technical Field
The invention belongs to the technical field of biological detection, and particularly relates to a screening and quantitative detection method for common herbicides in blood.
Background
The herbicide is widely applied in the modern agricultural production process, the production quantity and the use quantity of the herbicide are increased year by year, and the current common herbicides in China comprise more than 20 types such as quaternary ammonium salt, organic phosphorus, amide, sulfonylurea, triazobenzene and the like. However, the cases of poisoning caused by the herbicide are increased, and the rapid and accurate qualitative screening and quantitative analysis of the herbicide in blood are of great significance for detecting the related cases. Because of various types and properties of herbicides, sample pretreatment and instrument analysis methods are different. At present, the detection method of the herbicide in the biological detection material mainly comprises a liquid chromatography-mass spectrometry combined method, a capillary electrophoresis method, a thin layer chromatography, a gas chromatography-mass spectrometry combined method, an immunoassay method and the like. In the methods reported in the existing documents, conventional sample pretreatment methods such as liquid-liquid extraction and solid-phase extraction can only extract a certain number of herbicides with similar properties from blood, most of the methods are only suitable for detecting a single type of herbicide, and the detection methods for screening and quantifying a plurality of types of herbicides are only reported, so that the requirements for simultaneously screening and quantifying the plurality of types of herbicides cannot be met, and the types and the content of the herbicides in blood of a poisoned person cannot be quickly judged.
Disclosure of Invention
Aiming at the technical problems that only a single type of herbicide can be extracted from blood and most of the herbicides are only suitable for detection of the single type of herbicide in the prior art, the invention provides a method for screening and quantitatively detecting common herbicides in blood.
The invention also provides application of the method in analyzing the types and the contents of the herbicides in blood samples in the process of determining toxic death causes.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a method for screening and quantitatively detecting common herbicides in blood comprises pretreating blood sample by protein precipitation method, and detecting herbicides in the blood sample by liquid chromatography/high-resolution mass spectrometry.
Compared with the prior art, the protein precipitation method is used for pretreating the blood sample, so that protein precipitation interfering with measurement can be removed, the herbicide to be measured is still remained in the blood sample, and the liquid chromatography/high-resolution mass spectrometry combined analysis method is matched, so that various herbicides in the blood can be screened quickly, simply and conveniently at the same time.
Preferably, the specific operation steps of the protein precipitation method are as follows: adding a protein precipitator with a volume 4-5 times that of the blood sample into the blood sample, performing vortex for 60-90 s, performing ultrasonic treatment for 5-10 min, centrifuging at 10000-12000 rpm/min for 10-15 min, and taking supernatant to obtain the blood sample; wherein the protein precipitant is 75 v/v% acetonitrile aqueous solution. The precipitant does not react with herbicide, does not interfere with measurement, and can completely precipitate protein in blood sample.
Preferably, in the combined analysis method of liquid chromatography and high resolution mass spectrometry, the chromatographic conditions of the liquid chromatography are as follows:
a chromatographic column: octadecylsilane chemically bonded silica chromatographic column;
mobile phase a was 0.1% formic acid solution and mobile phase B was methanol, and the elution was performed with a linear gradient as follows:
flow rate: 0.3 mL/min.
The preferred chromatographic column and mobile phase provide the liquid phase detection method with higher sensitivity, accuracy and reproducibility. Such as Hypersil GOLD C-18 chromatographic column, the obtained chromatographic peak has sharp and symmetrical peak shape, and all substances can be completely separated, and the signal-to-noise ratio is high. The preferential elution gradient can ensure that different herbicides have different respective peak-out time, peak shapes and separation effects, and is convenient for comparative observation, so that the types and the concentrations of the herbicides in the blood samples can be accurately judged. When the volume ratio of the mobile phase 0.1% formic acid solution/methanol is 95: and 5, the separation effect is best, the ionization effect is strongest, and the sensitivity is highest.
Preferably, the analysis conditions of the high resolution mass spectrum are as follows:
an ion source: a source of HESI;
electrospray voltage: 3200V;
capillary temperature: 320 ℃;
temperature of the auxiliary heater: 300 ℃;
sheath gas: nitrogen with the flow rate of 30L/min;
auxiliary gas: nitrogen with the flow rate of 15L/min;
data scanning mode: the system comprises a positive-negative switching primary full scanning/real-time secondary mass spectrum scanning mode, wherein the resolution of the primary full scanning mode is 70000, and the resolution of the secondary scanning mode is 17500.
The high-resolution mass spectrum has stronger specificity, higher sensitivity, accuracy and reproducibility, and more accurate detection result.
Preferably, the kind of the herbicide includes at least one of quaternary ammonium salts, organophosphates, triazines, imidazolinones, amides, sulfonylureas, diphenylethers, phenoxy carboxylic acids, benzoic acids, aryloxyphenoxypropionic acids, dinitroanilines, picolinic acids, and cyclohexenone. The above herbicide classes are those that are common in herbicide poisoning situations.
Preferably, the quaternary ammonium salt-type herbicide includes at least one of paraquat and diquat; and/or
The organophosphorus herbicide comprises at least one of glyphosate and glufosinate; and/or
The triazine herbicide comprises at least one of cyanazine, atrazine, simazine, simetryn and prometryn; and/or
The imidazolinone herbicide is imazapyr; and/or
The amide herbicide comprises at least one of metazachlor, acetochlor and propisochlor; and/or
The sulfonylurea herbicide comprises at least one of chlorsulfuron, metsulfuron, bensulfuron-methyl and epoxysulfuron; and/or
The diphenyl ether herbicide is bentazone; and/or
The phenoxy carboxylic acid and benzoic acid herbicide is dicamba; and/or
The aryloxy phenoxy propionic acid herbicide comprises at least one of haloxyfop-methyl and quizalofop-ethyl; and/or
The dinitroaniline herbicide comprises at least one of pendimethalin and dimethomorph; and/or
The pyridine carboxylic acid herbicide is clopyralid; and/or
The cyclohexenone herbicide is diclofop-methyl.
The embodiment of the invention also provides application of the method in analyzing the types and the contents of the herbicides in blood samples in the process of forensic determination of toxic death causes. By the method, qualitative screening and quantitative analysis can be stably, quickly and accurately carried out on common herbicides in the blood sample to be detected, and the method has important significance for detecting herbicide poisoning related cases.
Drawings
FIG. 1 is an extracted ion chromatogram of paraquat in example;
FIG. 2 is an extracted ion chromatogram of diquat in an example;
FIG. 3 is a chromatogram of the extracted ions of glyphosate in an example;
FIG. 4 is an extracted ion chromatogram of glufosinate in the example;
FIG. 5 is an ion chromatogram obtained by extracting cyanazine in example;
FIG. 6 is an extracted ion chromatogram of atrazine in the example;
FIG. 7 is an extracted ion chromatogram of simazine in the example;
FIG. 8 is an extracted ion chromatogram of simetryn in the example;
FIG. 9 is an extracted ion chromatogram of prometryn in the example;
FIG. 10 is an extracted ion chromatogram of imazapyr in the examples;
FIG. 11 is an extracted ion chromatogram of metazachlor in the examples;
FIG. 12 is an extracted ion chromatogram of acetochlor in the example;
FIG. 13 is an extracted ion chromatogram of propisochlor in the example;
FIG. 14 is an extracted ion chromatogram of chlorsulfuron in the example;
FIG. 15 is an extracted ion chromatogram of metsulfuron-methyl in the example;
FIG. 16 is an extracted ion chromatogram of bensulfuron methyl in the example;
FIG. 17 is an extracted ion chromatogram of rimsulfuron in an example;
FIG. 18 is an extracted ion chromatogram of bentazon in the example;
FIG. 19 is an extracted ion chromatogram of dicamba in the example;
FIG. 20 is an extracted ion chromatogram of haloxyfop in example;
FIG. 21 is an extracted ion chromatogram of quizalofop-ethyl in example;
FIG. 22 is an extracted ion chromatogram of pendimethalin in an example;
FIG. 23 is an extracted ion chromatogram of dimethomorph in the example;
FIG. 24 is an extracted ion chromatogram of clopyralid in the example;
FIG. 25 is an extracted ion chromatogram of molinate in example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment of the invention provides a method for screening and quantitatively detecting common herbicides in blood, which comprises the following steps:
1. reagent
Paraquat, diquat, glyphosate, glufosinate, cyanazine, atrazine, simazine, simetryn, prometryn, imazapic acid, metazachlor, acetochlor, propisochlor, chlorsulfuron, metsulfuron, bensulfuron-methyl, sulfometuron, bentazone, dicamba, haloxyfop-methyl, quizalofop-ethyl, pendimethalin, dimethomole, clopyralid, diclofop-methyl standard were purchased from Shanghai city pesticide research institute Limited and were water or methanol standard solutions with a concentration of 1 mg/ml. Acetonitrile, methanol (chromatographically pure) were obtained from Thermo Fisher, usa, formic acid (chromatographically pure) was obtained from DIKMA, usa, and the experimental water was ultrapure water prepared by Milli-Q system (Millipore, usa).
2. Instrument for measuring the position of a moving object
Thermo ScientificTM Q ExactiveTMFocus ultra-high pressure liquid chromatography-high resolution mass spectrometer (Thermo Fisher, USA), high-speed refrigerated centrifuge (Thermo Fisher, USA), vortex oscillator (CORNING, USA), KQ-500DE type digital control ultrasonic cleaner (ultrasonic instruments, Inc., Kunshan).
3. Solution preparation
Mixing standard substance stock solution: accurately sucking 50 mu L of each standard solution into the same volumetric flask, using purified water to fix the volume to 10mL to obtain mixed standard substance stock solution with each standard quality concentration of 5 mu g/mL, and storing the mixed standard substance stock solution in a refrigerator at 4 ℃ for later use.
Mixing standard substance working solution: and diluting 5 mu g/mL of mixed standard substance stock solution by using a mobile phase step by step to prepare mixed standard substance working solution with the standard quality and concentration of 4000ng/mL, 3000ng/mL, 2000ng/mL, 1000ng/mL, 500ng/mL, 100ng/mL, 50ng/mL, 20ng/mL, 10ng/mL, 5ng/mL, 1ng/mL and 0.5ng/mL respectively.
Mobile phase: mobile phase A: diluting 2mL of formic acid to 2000mL with ultrapure water to obtain a 0.1% formic acid solution; mobile phase B: pure methanol.
Protein precipitant: acetonitrile/water (3: 1, v/v).
4. Sample pretreatment
Dividing the experimental blood into 12 parts, and adding the mixed standard substance working solution to obtain the standard blood containing standard solutions with different concentrations. Taking 200 mu L of labeled blood, respectively adding 800 mu L of acetonitrile/water (3: 1, v/v) mixed solvent, vortexing for 1min, performing ultrasonic treatment for 5min, centrifuging at 12000r/min to precipitate protein for 10min, taking supernatant, filtering with 0.2 mu m filter membrane, and performing liquid chromatography/high resolution mass spectrometry.
5. Liquid chromatography and high resolution mass spectrometry conditions
5.1 high resolution liquid chromatography conditions:
a chromatographic column: a Security Guard C-18 pre-column (10X 4mm, 3 μm, Thermo Fisher USA), a Hypersil GOLD C-18 column (100X 2.1mm, 1.9 μm, Thermo Fisher USA).
Column temperature: and (4) room temperature.
Linear elution was used, with the following gradient:
flow rate: 0.3mL/min, and the sample size is 1. mu.L.
The chromatogram for each herbicide is shown in figure 1.
5.2 the conditions of the high resolution mass spectrometry are as follows:
an ion source: a source of HESI;
electrospray voltage: 3200V;
capillary temperature: 320 ℃;
temperature of the auxiliary heater: 300 ℃;
sheath gas: nitrogen with the flow rate of 30L/min;
auxiliary gas: nitrogen with the flow rate of 15L/min;
data scanning mode: positive and negative switching Full scan/real time secondary mass spectrometry scan (Full MS/dd-MS)2) The resolution of the mode, primary full scan mode (50-750) is 70000 and the resolution of the secondary scan mode (dd-MS2) is 17500.
A single standard substance with the concentration of 1 mu g/mL is analyzed through continuous injection, the precursor and the secondary ions of each target substance are detected, and the mass spectrum parameters and the ion chromatogram extraction result of the detection are shown in Table 1.
6. Methodology investigation
6.1 Linear relationship with detection Limit
And (3) measuring the mixed standard substance working solution and the mixed standard solution under the conditions of 5.1 and 5.2, and drawing a linear relation curve by quantifying the peak area of the ion pair to the mass concentration. The results show that the linear relationship of the herbicides in the range tested is good, and the correlation coefficient (R) is good2) Are all greater than 0.995. The detection Limit (LOD) is in the range of 0.5-50 ng/ml, and the linear regression equation, the correlation coefficient and the detection limit are shown in Table 2.
TABLE 2
6.2 recovery and precision
Selecting blank samples, accurately adding 3 concentration levels of mixed standard working solutions respectively, processing according to a pretreatment method of 4, parallelly measuring 6 parts, detecting under the conditions of 5.1 and 5.2, and calculating average recovery rate, relative standard deviation of measured values and day-to-day precision. The results showed that the average recovery of the target was 67.4% to 119.13% for each target, the relative standard deviation (n 6) was 0.66% to 10.78%, the daily precision (n 6) was 9.12% or less, and the daily precision (n 3) was 10.46% or less, as shown in table 3.
TABLE 3
Example 2
Blood samples of 10 suspected herbicide toxicities were tested as described in example 1.
Protein precipitation was performed on the blood sample to be tested by the pretreatment method used in 4 of example 1, and detection was performed under the conditions of 5.1 and 5.2, whereby 7 cases of paraquat (blood concentration of 0.09 to 78.48. mu.g/ml), 1 case of glyphosate (blood concentration of 0.79. mu.g/ml), 1 case of atrazine (blood concentration of 4.73ng/ml) and 1 case of acetochlor (blood concentration of 10.57ng/ml) were detected.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A screening and quantitative detection method for common herbicides in blood is characterized in that a blood sample is pretreated by a protein precipitation method, and the herbicides in the blood sample are detected by a liquid chromatography/high-resolution mass spectrometry combined analysis method; the herbicide is quaternary ammonium salt, organophosphorus, triazine, imidazolone, amide, sulfonylurea, diphenyl ether, phenoxy carboxylic acid, benzoic acid, aryloxy phenoxy propionic acid, dinitroaniline, pyridine carboxylic acid and cyclohexenone; the quaternary ammonium salt herbicide is paraquat and diquat; the organic phosphorus herbicide is glyphosate and glufosinate; the triazine herbicide is cyanazine, atrazine, simazine, simetryn and prometryn; the imidazolinone herbicide is imazapyr; the amide herbicide is metazachlor, acetochlor and propisochlor; the sulfonylurea herbicide is chlorosulfuron, metsulfuron-methyl, bensulfuron-methyl and epoxysulfuron-methyl; the diphenyl ether herbicide is bentazone; the phenoxy carboxylic acid and benzoic acid herbicide is dicamba; the aryloxy phenoxypropionic acid herbicide is haloxyfop-methyl and quizalofop-ethyl; the dinitroaniline herbicide is pendimethalin and dimethomorph; the pyridine carboxylic acid herbicide is clopyralid; the cyclohexenone herbicide is diclofop-methyl;
in the combined analysis method of the liquid chromatogram and the high resolution mass spectrum, the chromatographic conditions of the liquid chromatogram are as follows:
a chromatographic column: octadecylsilane chemically bonded silica chromatographic column;
mobile phase a was 0.1% formic acid solution and mobile phase B was methanol, and the elution was performed with a linear gradient as follows:
2. the method for screening and quantitatively detecting the common herbicides in blood as claimed in claim 1, wherein the specific operation steps of the protein precipitation method are as follows: adding a protein precipitator with a volume 4-5 times that of the blood sample into the blood sample, performing vortex for 60-90 s, performing ultrasonic treatment for 5-10 min, centrifuging at 10000-12000 rpm/min for 10-15 min, and taking supernatant to obtain the blood sample; wherein the protein precipitator is 70-80 v/v% acetonitrile water solution.
3. The method for screening and quantitatively detecting common herbicides in blood as claimed in claim 1, wherein in the combined analysis method of liquid chromatography and high resolution mass spectrometry, the analysis conditions of the high resolution mass spectrometry are as follows:
an ion source: a source of HESI;
electrospray voltage: 3200V;
capillary temperature: 320 ℃;
temperature of the auxiliary heater: 300 ℃;
sheath gas: nitrogen with the flow rate of 30L/min;
auxiliary gas: nitrogen with the flow rate of 15L/min;
data scanning mode: the system comprises a positive-negative switching primary full scanning/real-time secondary mass spectrum scanning mode, wherein the resolution of the primary full scanning mode is 70000, and the resolution of the secondary scanning mode is 17500.
4. The use of the method of claim 1 for screening and quantitatively detecting common herbicides in blood for analyzing the types and contents of herbicides in blood samples during forensic determination of cause of death due to poisoning.
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