CN111751466A - Method for simultaneously determining DON toxin and NIV toxin - Google Patents
Method for simultaneously determining DON toxin and NIV toxin Download PDFInfo
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- CN111751466A CN111751466A CN202010618732.2A CN202010618732A CN111751466A CN 111751466 A CN111751466 A CN 111751466A CN 202010618732 A CN202010618732 A CN 202010618732A CN 111751466 A CN111751466 A CN 111751466A
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- 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
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- 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
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention discloses a method for simultaneously determining DON toxin and NIV toxin in grains. The method for simultaneously detecting the DON toxin and the NIV toxin by using the liquid chromatograph after purifying the sample by using the multifunctional purifying column greatly shortens the experimental process and has higher recovery rate and precision. The method is simple, effective, economical and reliable, and provides a new technical guarantee for the safety of grain products.
Description
Technical Field
The invention belongs to the field of detection, relates to a method for determining mycotoxin in grains, and particularly relates to a method for simultaneously determining DON toxin and NIV toxin.
Background
Scab, also known as wheat "cancer", is a serious disease in wheat growing areas in the middle of China, has a complex pathogenesis, is generally caused by fusarium fungi, and infects wheat when the wheat spikes and flowers. The metabolic toxins of gibberella mainly comprise DON toxin and derivatives thereof, NIV toxin, ZEN toxin, FB toxin and the like, and more or less of the toxins affect the health safety of human beings and livestock.
Deoxynivalenol (DON toxin) is also called as vomitoxin because a series of symptoms such as diarrhea, dizziness, vomit, bellyache, nausea and the like can be produced after people or livestock contact with a certain amount of the toxin, has certain carcinogenicity, and is one of common mycotoxins of grain pollutants in China. Nivalenol (NIV toxin) is more toxic than DON toxin, and has certain effects on skin tissues, hematopoietic tissues, cardiovascular system and nervous system of livestock besides common vomiting symptoms. Therefore, the DON toxin is one of the national standards for the quality detection of wheat products, the national standard for the DON toxin in cereal crop products is 1000ug/kg, but the NIV toxin is not required to be too much, and the nation needs to prevent the NIV toxin in cereal agricultural products. The quantitative detection of DON toxin and NIV toxin is of great significance to the detection and determination of wheat quality.
With regard to the detection methods for DON toxins, these detection methods have so far been mostly mature and can be applied in the toxin detection of most wheat. Mainly includes Thin Layer Chromatography (TLC), Gas Chromatography (GC), gas chromatography-mass spectrometry (GC-MS), gas chromatography-electron capture detector (GC-ECD), High Performance Liquid Chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), enzyme linked immunosorbent assay (ELISA), and the like, and each of these methods has various advantages and disadvantages, and an experimenter can select an appropriate method for detection according to his/her needs. With respect to detection of NIV toxins, generally, NIV toxins are measured in conjunction with DON toxins. Detecting DON toxin and NIV toxin in the feed by using gas chromatography-mass spectrometry, wherein the detection limits of the two toxins are 6ng/g and 8ng/g respectively after silanization derivatization; the detection limit of NIV toxin detected by Zhang Wei ever by a solid phase extraction-high performance liquid chromatography tandem mass spectrometry combined method is 2 ug/kg; the average detection limit of NIV toxin in wheat by Marigong et al is 182.56ug/kg by ultra performance liquid chromatography-tandem mass spectrometer. In terms of the current technology, most methods for measuring the NIV toxin in the grain measurement can measure the DON toxin, but the method for measuring the DON toxin can detect the NIV toxin, but the recovery rate is low. Therefore, in order to ensure the efficiency and safety of the measurement of grains such as wheat, it is very meaningful to develop methods which can simultaneously detect DON toxin and NIV toxin.
At present, no report exists on a method for simultaneously detecting DON toxin and NIV toxin by using a C18 chromatographic column high performance liquid chromatography separation detection to purify a wheat grain sample by using a Mycosep #227 multifunctional purification column and a Mycosep #226 multifunctional purification column.
Disclosure of Invention
The invention mainly aims to solve the problems of low efficiency, inaccurate measuring result, complex experimental process and the like of DON toxin and NIV toxin detection in the measurement of grains such as wheat and the like, and provides a novel method for simultaneously measuring DON toxin and NIV toxin, which is convenient to operate and accurate in result.
The invention provides a method for simultaneously determining DON toxin and NIV toxin in grains, which comprises the following steps:
the DON toxin represents deoxynivalenol;
the NIV toxin represents nivalenol;
1) placing a grain sample to be detected in a solvent for ultrasonic extraction, filtering and collecting filtrate;
2) loading the filtrate obtained in the step 1) on a multifunctional purification column, collecting effluent liquid, drying, adding a mobile phase for dissolving, filtering and collecting the filtrate;
3) drawing a standard curve:
detecting the standard substance solution by high performance liquid chromatography, collecting effluent liquid, fitting by taking each standard peak area as a vertical coordinate and the concentration of the standard substance solution as a horizontal coordinate, wherein the unit is ug/ml, and obtaining a standard curve of the DON toxin and the NIV toxin;
the standard solution is a DON toxin standard solution and an NIV toxin standard solution;
4) and (3) determining the content of DON toxin and NIV toxin in the grain sample to be detected:
detecting the filtrate obtained in the step 2) by adopting a high performance liquid chromatography according to the same chromatographic detection conditions as the step 3), collecting effluent liquid, and comparing the ordinate of the effluent liquid with the standard curve obtained in the step 3) to obtain the content of the DON toxin and the NIV toxin in the grain sample to be detected.
In step 1) of the above method, the solvent is at least one selected from acetonitrile and water; specifically selected from a mixed solution consisting of acetonitrile and water; in the mixed solution, the volume ratio of acetonitrile to water is 80-90: 16; specifically 84: 16;
the dosage ratio of the grain sample to be detected to the solvent is 20-30 g: 100 mL; specifically, 25 g: 100 mL;
in the ultrasonic extraction step, the temperature is 30-38 ℃; in particular 35 ℃; the time is 20-40 min; specifically 30 min.
In the step 2), the multifunctional purifying column is Mycosep #227 or Mycosep # 226;
the dosage of the filtrate is 0.8-1 times of the column volume; specifically 10ml (i.e. 1 column volume);
in the blow-drying step, the temperature is 50-58 ℃; in particular to 55 ℃; the used equipment is a nitrogen blowing instrument;
the mobile phase is a mixed solution consisting of water, acetonitrile and methanol; the volume ratio of the water to the acetonitrile to the methanol is 90:5: 5;
in the filtering step, the aperture of the filter membrane is 0.22 um.
In the step 3), the detection conditions of the high performance liquid chromatograph are as follows:
a chromatographic column: c18 column, 250mm × 4.6mm,5 um;
isocratic elution mobile phase: a mixed solution consisting of water, acetonitrile and methanol in a volume ratio of 90:5: 5;
flow rate: 1.0 ml/min;
detection wavelength: λ 218 nm;
column temperature: 40 ℃;
sample introduction amount: 20 ul.
In the step 3), the DON toxin with the retention time of 14.7099min is obtained;
the NIV toxin with a retention time of 7.407 min.
In the step 3), the obtained DON toxin standard curve is Y-25.5029X-3.7918
The standard curve of the obtained NIV toxin is Y-41.3470X + 3.0784;
wherein Y is a standard peak area; x is the concentration of the solution in ug/ml.
The invention provides a method for simultaneously detecting DON toxin and NIV toxin. The method is convenient and rapid to operate, can save cost, and has relatively accurate result and excellent recovery rate and linear relation.
Drawings
FIG. 1 is a chromatogram of flow rates of 1.0ml/min, 0.8ml/min, 0.6 ml/min;
FIG. 2 is a chromatogram at a column temperature of 45 ℃, 40 ℃, 35 ℃, 30 ℃ and 25 ℃;
FIG. 3 is a chromatogram of 5ul, 10ul, 15ul and 20ul samples;
FIG. 4 is a chromatogram at wavelengths 218nm and 220 nm.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
Materials and methods
1.1 Main instruments and reagents
TABLE 1 Main instruments and reagents
1.2 standards and reagents
TABLE 2 standards and reagents
Experimental methods
2.1 pretreatment of test articles
Accurately weighing 25g (to the nearest 0.01g) of sample into a 250ml triangular flask, adding 100ml acetonitrile: an aqueous solution (84/16, v/v). Followed by ultrasonic extraction at 35 ℃ for 30min, standing and filtration through a quantitative filter paper.
10ml of the filtrate is taken and transferred to a Mycosep #227 or Mycosep #226(romer) multifunctional purification column for treatment. Sucking 4ml of the treated effluent liquid, placing the effluent liquid in a glass tube, and drying the effluent liquid by using a nitrogen blowing instrument at the temperature of 55 ℃. The glass tube was then removed and dissolved in 1ml of mobile phase (water: acetonitrile: methanol: 90:5:5, v/v/v) and filtered through a 0.22um organic filter for analysis.
Detecting and analyzing the sample to be analyzed in the step (2) by a high performance liquid chromatograph, and then obtaining the content results of the DON toxin and the NIV toxin in the sample to be analyzed
The specific chromatographic conditions in step (3) are as follows:
chromatographic column C18 column (250 mm × 4.6mm,5 um);
isocratic elution mobile phase, water, acetonitrile, methanol (90:5:5, v/v/v);
the flow rate is 1.0 ml/min;
the detection wavelength is lambda-218 nm;
the column temperature is 40 ℃;
the sample amount is 20 ul.
Results and discussion
3.1 optimization of pretreatment
Through continuous experimental comparison and demonstration, the invention inspects the experimental effects of two multifunctional purifying columns, namely, a solid-phase purifying column Mycosep #227 and a Mycosep #226, and the results show that the two multifunctional purifying columns have excellent effects on the purifying effects of DON and NIV, and the deviation of the experimental results is relatively small, and the relative standard deviation is respectively 2.2% and 2.7%. Therefore, the two solid-phase purification columns are selected as experimental materials in the purification and filtration process of the toxin in the pretreatment.
3.2 chromatographic Condition selection
Three flow rates, 1.0ml/min, 0.8ml/min, and 0.6ml/min, were selected for the experiments (FIG. 1). The result shows that the flow rate has an influence on the retention time but has a small influence on the peak area, namely the flow rate has an influence on the experimental rate but has a small influence on the experimental result, the experimental flow of the flow rate system of 1.0ml/min is 4min and 10min which are shortened relative to 0.8ml/min and 0.6ml/min, and therefore the flow rate system of 1.0ml/min with a faster flow rate is selected in the flow rate selection through comprehensive consideration;
and then five column temperatures of 45 ℃, 40 ℃, 35 ℃, 30 ℃,25 ℃ and the like are selected for carrying out test experiments, and the experimental result shows that (figure 2) the column temperature has only slight influence on the peak area but has larger influence on the retention time, namely the column temperature has little influence on the toxin determination result but has higher column temperature and faster experimental rate. However, the service life of the chromatographic column can be influenced by overhigh column temperature, so that the invention adopts the column temperature of 40 ℃ as a proper chromatographic condition by comprehensive consideration;
the influence of the sample injection amount on a substance detection result is large, the slit width of the detection result is increased when the sample injection amount is too large, a tailing peak condition sometimes occurs, and the harm of the too large sample injection amount on a chromatographic column is also large; on the contrary, when the amount of the sample is too small, the peak area becomes too small or even not present, and the detection is impossible. Therefore, in the present invention, four sample volumes such as 20ul, 15ul, 10ul, 5ul, etc. are selected to perform the comparison test (fig. 3) within the range of the column, and it is found that the influence of the sample volume on the retention time is small, and when the sample volume is 20ul, the peak shape of the detection result is the best, and the peak area is gradually reduced with the reduction of the sample volume. Therefore, the invention selects 20ul as the sample size of the experiment;
since the absorption spectra of the substances to be detected are different, different wavelengths are selected as detection conditions in the detection of the substances. However, in the present invention, the absorption spectra of DON and NIV are relatively close to each other, and therefore, the comparison test was conducted between the wavelengths of 218nm and 220nm, which are commonly used in the conventional combined detection (FIG. 4). As a result, it was found that the difference between the results of the experiments was not so large, and the retention time was not so much affected, and the wavelength 218nm was selected as the detection wavelength because the response value was slightly larger when the wavelength 218nm was selected for detection.
3.3 Linear Range of the method
Standard mycotoxin solution with certain concentration is added into 5 blank matrixes to prepare standard working solution, namely 10ug/ml, 8ug/ml, 5ug/ml, 4ug/ml and 2 ug/ml. The solution was analyzed under the above experimental conditions, and the analysis results are shown in table 3.
TABLE 3 DON, NIV Standard curves
Precision within 3.4 days and tightness between days
Standard working solutions of 8ug/ml, 5ug/ml and 4ug/ml were prepared according to the method of 3.3. Treating the solution according to 2.1 method within the same day, and horizontally repeating for 3 times to determine the precision within the day; day precision was determined by treating the solution for 5 consecutive days according to 2.1 and repeating the levels three times. The measurement results are shown in Table 4.
TABLE 4 repeatability, precision of DON, NIV
3.5 recovery, detection and quantitation limits
Preparing three standard working solutions with different concentrations of 10ug/kg, 100ug/ml, 1000ug/ml and the like according to the method of 3.3, treating the solutions by a method of 2.1, and determining the recovery rate of the experiment according to the results of three parts per level; the concentrations corresponding to the instrument signal-to-noise ratios of 3:1 and 10:1 are respectively the detection limit and the quantification limit of the detection method. The results of the experiment are shown in Table 5.
TABLE 5 recovery, detection limit, quantitation limit for DON, NIV
Conclusion
The method for simultaneously detecting the DON toxin and the NIV toxin by using the liquid chromatograph after purifying the sample by using the Mycosep #227 and Mycosep #226 multifunctional purifying columns greatly shortens the experimental process and has higher recovery rate and precision. The method is simple, effective, economical and reliable, and provides a new technical guarantee for the safety of grain products.
Claims (6)
1. A method for simultaneously determining DON and NIV toxins in a cereal comprising:
the DON toxin represents deoxynivalenol;
the NIV toxin represents nivalenol;
1) placing a grain sample to be detected in a solvent for ultrasonic extraction, filtering and collecting filtrate;
2) loading the filtrate obtained in the step 1) on a multifunctional purification column, collecting effluent liquid, drying, adding a mobile phase for dissolving, filtering and collecting the filtrate;
3) drawing a standard curve:
detecting the standard substance solution by high performance liquid chromatography, collecting effluent liquid, fitting by taking each standard peak area as a vertical coordinate and the concentration of the standard substance solution as a horizontal coordinate, wherein the unit is ug/ml, and obtaining a standard curve of the DON toxin and the NIV toxin;
the standard solution is a DON toxin standard solution and an NIV toxin standard solution;
4) and (3) determining the content of DON toxin and NIV toxin in the grain sample to be detected:
detecting the filtrate obtained in the step 2) by adopting a high performance liquid chromatography according to the same chromatographic detection conditions as the step 3), collecting effluent liquid, and comparing the ordinate of the effluent liquid with the standard curve obtained in the step 3) to obtain the content of the DON toxin and the NIV toxin in the grain sample to be detected.
2. The method of claim 1, wherein: in the step 1), the solvent is at least one selected from acetonitrile and water; specifically selected from a mixed solution consisting of acetonitrile and water; in the mixed solution, the volume ratio of acetonitrile to water is 80-90: 16; specifically 84: 16;
the dosage ratio of the grain sample to be detected to the solvent is 20-30 g: 100 mL; specifically, 25 g: 100 mL;
in the ultrasonic extraction step, the temperature is 30-38 ℃; in particular 35 ℃; the time is 20-40 min; specifically 30 min.
3. The method according to claim 1 or 2, characterized in that: in the step 2), the multifunctional purifying column is Mycosep #227 or Mycosep # 226;
the dosage of the filtrate is 0.8-1 times of the column volume; specifically 10 ml;
in the blow-drying step, the temperature is 50-58 ℃; in particular to 55 ℃; the used equipment is a nitrogen blowing instrument;
the mobile phase is a mixed solution consisting of water, acetonitrile and methanol; the volume ratio of the water to the acetonitrile to the methanol is 90:5: 5;
in the filtering step, the aperture of the filter membrane is 0.22 um.
4. A method according to any one of claims 1 to 3, wherein: in the step 3), the detection conditions of the high performance liquid chromatograph are as follows:
a chromatographic column: c18 column, 250mm × 4.6mm,5 um;
isocratic elution mobile phase: a mixed solution consisting of water, acetonitrile and methanol in a volume ratio of 90:5: 5;
flow rate: 1.0 ml/min;
detection wavelength: λ 218 nm;
column temperature: 40 ℃;
sample introduction amount: 20 ul.
5. The method according to any one of claims 1 to 4, wherein: in the step 3), the DON toxin with the retention time of 14.7099min is obtained;
the NIV toxin with a retention time of 7.407 min.
6. The method according to any one of claims 1 to 5, wherein: in the step 3), the obtained DON toxin standard curve is Y-25.5029X-3.7918
The standard curve of the obtained NIV toxin is Y-41.3470X + 3.0784;
wherein Y is a standard peak area; x is the concentration of the solution in ug/ml.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113009020A (en) * | 2021-02-26 | 2021-06-22 | 安徽农业大学 | Method for simultaneously determining DON toxin, NIV toxin and ZEN toxin in grains |
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| SU1364979A1 (en) * | 1986-06-19 | 1988-01-07 | Институт питания АМН СССР | Method of quantitative determination of desoxynovalinol in cereals and products of processing thereof |
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2020
- 2020-06-30 CN CN202010618732.2A patent/CN111751466A/en active Pending
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| CN102297902A (en) * | 2010-06-25 | 2011-12-28 | 中国医学科学院药用植物研究所 | Method for detecting nivalenol and deoxynivalenol (DON) toxins in traditional Chinese medicine |
| CN102507774A (en) * | 2011-10-31 | 2012-06-20 | 江苏省农业科学院 | Extracting, purification and detection method for nivalenol in grains |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113009020A (en) * | 2021-02-26 | 2021-06-22 | 安徽农业大学 | Method for simultaneously determining DON toxin, NIV toxin and ZEN toxin in grains |
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