CN113203702A - Method for measuring content of aflatoxin B1 in alfalfa forage grass - Google Patents
Method for measuring content of aflatoxin B1 in alfalfa forage grass Download PDFInfo
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- CN113203702A CN113203702A CN202110405804.XA CN202110405804A CN113203702A CN 113203702 A CN113203702 A CN 113203702A CN 202110405804 A CN202110405804 A CN 202110405804A CN 113203702 A CN113203702 A CN 113203702A
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- OQIQSTLJSLGHID-WNWIJWBNSA-N aflatoxin B1 Chemical compound C=1([C@@H]2C=CO[C@@H]2OC=1C=C(C1=2)OC)C=2OC(=O)C2=C1CCC2=O OQIQSTLJSLGHID-WNWIJWBNSA-N 0.000 title claims abstract description 59
- 229930020125 aflatoxin-B1 Natural products 0.000 title claims abstract description 59
- 239000004459 forage Substances 0.000 title claims abstract description 58
- 241000219823 Medicago Species 0.000 title claims abstract description 43
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 title claims abstract description 43
- 239000002115 aflatoxin B1 Substances 0.000 title claims abstract description 42
- 244000025254 Cannabis sativa Species 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
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- 101100449517 Arabidopsis thaliana GRH1 gene Proteins 0.000 claims description 17
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
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- IAWPVNMEXASPFO-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)[SiH3].[C] Chemical group C(CCCCCCCCCCCCCCCCC)[SiH3].[C] IAWPVNMEXASPFO-UHFFFAOYSA-N 0.000 claims description 2
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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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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Abstract
The invention discloses a method for measuring the content of aflatoxin B1 in alfalfa forage grass, which comprises the following steps: adding a magnetic molecularly imprinted nano material into a alfalfa forage grass solution to be detected, adjusting the pH value to 7.5, uniformly stirring, performing ultrasonic extraction at room temperature, layering the magnetic molecularly imprinted nano material under the action of an external magnetic field, removing a supernatant, and analyzing the magnetic molecularly imprinted nano material by using near-infrared diffuse reflection spectroscopy; and desorbing the aflatoxin B1 from the magnetic molecularly imprinted nanomaterial by using methanol, determining the aflatoxin B1 by using the desorption liquid through ultra-high performance liquid chromatography, and finally establishing a quantitative relation between the near-infrared diffuse reflection spectrum and the ultra-high performance liquid chromatography result so as to determine the content of trace aflatoxin B1 in the unknown alfalfa forage sample. The magnetic molecular imprinting nano material is used for measuring the content of the aflatoxin B1 in the alfalfa forage grass, and has the advantages of simple and convenient operation, low cost, high sensitivity and the like.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a method for determining the content of aflatoxin B1 in alfalfa forage grass.
Background
Mildew is a worldwide hazard that causes a large amount of waste of feed. According to the food and agriculture organization estimation of the United nations, about 5% -7% of the feed is eroded by fungi and mildewed every year around the world. The fungus produces secondary toxic metabolite mycotoxin in the growth and reproduction process, and the feed polluted by the toxin of the toxin-producing fungus and the toxin of the toxin-producing fungus can cause poisoning and certain chronic diseases.
Aflatoxins (Aflatoxins) are a class of secondary mycotoxins produced by aspergillus flavus or aspergillus parasiticus. Aflatoxins which pollute food mainly comprise aflatoxins B1, B2, G1, G2, M1 and the like. In naturally polluted food, aflatoxin B1 (namely AFB1) has the highest toxicity, and the dairy cow can convert aflatoxin B1 in the feed into aflatoxin M1 in the dairy product, thereby bringing about the food safety problem of the dairy product and the dairy product. Aflatoxin B1 was detected in food and forage grasses at higher detection rates and levels, especially in high temperature and high humidity areas.
At present, methods for detecting aflatoxin in various foods are established, such as a liquid-mass combination method, a high performance liquid chromatography method, an enzyme-linked immunosorbent assay and the like. In which the enzyme-linked immunosorbent antibody and other consumables are expensive, and the liquid-mass spectrometry and high performance liquid chromatography require pre-column or post-column derivatization to improve the sensitivity of the method, which increases the detection cost. Meanwhile, IAC is adopted in sample pretreatment methods specified by national standards to extract and purify aflatoxin, and although the pretreatment methods are high in sensitivity and good in selectivity, the cost is high, and the operation is complicated. Therefore, the method for extracting the aflatoxin in the forage grass by a sensitive, economical and rapid method is necessary to be explored.
Disclosure of Invention
Aiming at the defects of the technology, the invention aims to provide a method for measuring the content of aflatoxin B1 in alfalfa forage grass, so as to solve the problems of high cost and low selectivity in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for measuring the content of aflatoxin B1 in alfalfa forage grass comprises the following steps: the method comprises the steps of treating planted or purchased alfalfa forage grass as a bulk product, collecting sub-samples according to a system sampling method and according to the same time, space or quality interval, randomly collecting the first sub-sample in the first interval, and collecting the rest sub-samples according to the selected interval. The mass fraction of the ash content of the alfalfa forage is used for representing the sampling precision, the ash content precision A is +/- (1% -5%), the ash content standard deviation S is +/- (2% -3%), the number of the collected subsamples is n, and the establishment of the number of the subsamples is determined by the standard deviation S and the sampling precision A of a single subsample
(1) Preparing alfalfa forage grass solutions to be detected of different samples: crushing each alfalfa forage sample for at least 10 seconds, sieving the alfalfa forage sample by a 60-mesh sieve to ensure the uniformity of the sample, weighing 5g of the solid forage sample into a 50mL plastic centrifuge tube, adding 20mL of mixed solution (75:25, v/v) of methanol and water, carrying out ultrasonic extraction for 30min, centrifuging the mixture for 5min at 10000rpm, and taking the supernatant for later use.
(2) Preparing a magnetic molecularly imprinted nano material;
(3) taking 20ml of forage grass solution to be detected, and adding magnetic molecularly imprinted nanoparticles AFB1-Ba3V2O8(Eu) @ PDA15mg, adjusting the pH value to 7.5, stirring uniformly by ultrasonic adsorption, layering the mixed solution under the action of an external magnetic field, removing supernatant, carrying out diffuse reflection measurement on lower-layer precipitate by using a near-infrared spectrometer, dispersing the magnetic molecular imprinting nano material in the solution in an ultrasonic auxiliary mode, effectively separating a target object from an interfering object, and rapidly settling the imprinting material through the external magnetic field to achieve the purpose of efficient purification, wherein the imprinting material is not separated from the solution in a centrifugal or filtering mode, so that the method is more convenient and economic;
(4) desorbing aflatoxin B1 from the magnetic molecularly imprinted nanomaterial with methanol, layering under the action of an external magnetic field, collecting supernatant, and absorbing a small amount of desorption solution to determine aflatoxin B1 by ultra-high performance liquid chromatography;
(5) repeating the steps 1-4 for different samples to be tested according to the alfalfa forage grass solution and the magnetic molecularly imprinted nanoparticles AFB1-Ba in the step 33V2O8And (Eu) @ PDA combined near infrared diffuse reflection spectrogram and the near infrared spectrum linear model established by the ultra-high performance liquid chromatography result after elution in the step 4 to obtain the content of aflatoxin B1 in the forage.
Further, the ultrasonic extraction adsorption time is 5 min.
Further, the external magnetic field is a magnet as an external magnetic field source.
Further, the desorption solution in step 4 is methanol, and 2ml of methanol is used for desorption twice, and each time is 1 min.
Further, a Fourier transform near-infrared spectrometer is used for collecting the spectrum information of the magnetic molecularly imprinted nanoparticles adsorbing the aflatoxin B1. The method specifically comprises the following steps: selecting an absorption mode to collect a sample diffuse reflection spectrum, wherein the spectrum scanning range is 10000-4000cm-1Resolution of 16cm-1The number of scans was 32, and each sample was scanned 3 times in a repetition, and the average spectrum was calculated.
The implementation of the spectral preprocessing comprises: and carrying out derivative processing, standard normal variable transformation, trend-removing analysis and other processing on the diffuse reflection original spectrum, associating a near infrared spectrum value with an ultra performance liquid chromatography chemical value by using OPUS spectrum software, establishing a near infrared spectrum linear model by using a partial least square method, and optimizing and evaluating the model. Magnetic molecularly imprinted nanoparticles AFB1-Ba for representative alfalfa forage grass sample solutions3V2O8After the combination of (Eu) @ PDA, a Fourier transform near-infrared spectrometer is used for collecting the diffuse reflection spectrum of the magnetic nanoparticles adsorbing the forage grass AFB1, the supernatant after methanol elution is detected by using an ultra-high performance liquid chromatography, a model is established according to the near-infrared spectrum result and the liquid chromatography result, and the model is optimized and evaluated.
Furthermore, the detection conditions of the high performance liquid chromatography are that a chromatographic column is a C18 column, and the particle size of the carbon octadecylsilane chemically bonded silica is 5 mu m. The mobile phase comprises acetonitrile, methanol and 0.1 percent of formic acid aqueous solution by volume ratio of 20:30: 50. The excitation wavelength of the fluorescence detector is 360nm, and the emission wavelength is 440 nm.
The magnetic molecularly imprinted nano material is prepared by the following method:
synthesis of europium-doped barium vanadate nanoparticles
At room temperature, composite hydroxide (NaOH/KOH) 9 g in total was uniformly mixed at a molar ratio of 51.5: 48.5 and placed in a 25mL Teflon tube with a cap; adding 0.5mmol BaCl2And 0.5 mmoleV2O5After uniform mixing, adding a trace amount of europium nitrate as a dopant, and pouring into a Teflon tube; placing Teflon tube intoSealing the autoclave, and then putting the autoclave into a muffle furnace preheated to 200 ℃ for heat preservation for 13 hours; and (3) after heat preservation, taking out the autoclave, naturally cooling to room temperature, dissolving the product in deionized water, washing, filtering, collecting and removing hydroxide on the surface of the product, then washing for a plurality of times by using deionized water and absolute ethyl alcohol, and finally drying at 60 ℃ to obtain a white barium vanadate europium-doped sample.
Synthesis of barium vanadate europium-doped magnetic molecularly imprinted material
0.2g of barium vanadate europium-doped nano-material particles were weighed into a 250mL three-necked flask, and 80mL of Tris-HCl buffer solution (10mM, pH 8.5) was added. And mechanically stirring for 1 hour at room temperature until the barium vanadate europium-doped nano material particles are uniformly dispersed in the buffer solution. Then 5mL of template molecule AFB1 with the concentration of 2 mu g/mL is added, and the stirring is continued for 2 hours, so that AFB1 is better contacted with the surface of barium vanadate europium-doped nano material particles. Subsequently, 100mg of dopamine hydrochloride was added and the reaction was continued with stirring for 4 h. Finally, the solid product is separated from the solution under the action of the external magnet. Washing the product with ultrapure water for 5 times to remove unreacted dopamine, washing with 6% acetic acid-60% methanol solution (v/v) until AFB1 is not detected by liquid chromatography, washing with ultrapure water for 5 times to make the solution neutral, and obtaining AFB1-Ba3V2O8Drying the (Eu) @ PDA magnetic molecularly imprinted material at 60 ℃ for 6h in vacuum; because polydopamine is stable in solution and has good compatibility with aflatoxin, a polymer film containing active functional groups can be formed on the surface of the magnetic molecularly imprinted composite material, and further functionalization for effectively extracting aflatoxin can be realized.
Compared with the prior art, the technology of the invention has the following beneficial effects:
aiming at the characteristics that a forage grass component system is complex and aflatoxin content is extremely low and the characteristic that a magnetic material enhances near infrared spectrum signals, the magnetic molecularly imprinted nano-particle AFB1-Ba with high sensitivity is established3V2O8Content determination research of aflatoxin B1 by using (Eu) @ PDA-near infrared diffuse reflection-high performance liquid chromatography fluorescence method, AFB1-Ba3V2O8(Eu) @ PDA magnetic molecularly imprinted nanoparticles and ultra-high performance liquid chromatography-fluorescence detection method are combinedThe sensitivity of the method is further improved, and the detection limit of the aflatoxin B1 is 0.18pg/mL, which is lower than that of the national standard method.
According to the invention, reagent consumables such as a purification column and an antibody are not required, the magnetic molecularly imprinted nanoparticles can be desorbed and then recycled for 10 times, and the method has the advantage of low cost. The adsorption pre-enrichment of the forage grass aflatoxin B1 by the magnetic molecularly imprinted nanomaterial can be used for directly collecting near-infrared diffuse reflectance spectra without elution, and a possible, rapid and convenient method is provided for quantitative analysis of aflatoxin B1 in alfalfa forage grass solution.
The functionalized magnetic molecularly imprinted nanoparticle AFB1-Ba3V2O8The (Eu) @ PDA has a spatial structure suitable for aflatoxin B1, has high specificity, good selectivity for aflatoxin B1, and superparamagnetism, and is an ideal solid phase adsorbent in the pretreatment aspect of trace aflatoxin B1 samples.
Drawings
FIG. 1 is a schematic flow chart of a method for rapidly detecting aflatoxins in alfalfa forage grass in the practice of the invention.
FIG. 2 is a correlation map of the true value and the predicted value of aflatoxin B1.
Detailed Description
The following is further detailed by way of specific embodiments:
as shown in figure 1 and figure 2, the embodiment of the invention provides a method for measuring the content of aflatoxin B1 in alfalfa forage grass,
the alfalfa forage used in the embodiment of the invention is provided by Wuling mountain pasture of Chongqing Tianyou group.
In the embodiment of the invention, the external magnetic field is taken as an external magnetic field source by a magnet block with the size of 150mm multiplied by 120mm multiplied by 30mm close to the beaker.
Examples
Magnetic molecularly imprinted nanoparticle AFB1-Ba3V2O8Preparation of (Eu) @ PDA
Synthesis of europium-doped barium vanadate nanoparticles
At room temperature, a total of 9 g of composite hydroxide (NaOH/KOH) was addedUniformly mixing the materials according to the molar ratio of 51.5: 48.5, and putting the mixture into a 25mL Teflon tube with a cover; 0.5mmol of BaCl2And 0.5mmol V2O5After uniform mixing, adding a trace amount of europium nitrate as a dopant, and pouring into a Teflon tube; placing the Teflon tube into an autoclave, sealing, and placing the autoclave into a muffle furnace preheated to 200 ℃ for heat preservation for 13 hours; and (3) after heat preservation, taking out the autoclave, naturally cooling to room temperature, dissolving the product in deionized water, washing, filtering, collecting and removing hydroxide on the surface of the product, then washing for a plurality of times by using deionized water and absolute ethyl alcohol, and finally drying at 60 ℃ to obtain a white barium vanadate europium-doped sample.
Synthesis of barium vanadate europium-doped magnetic molecularly imprinted material
0.2g of barium vanadate europium-doped nano-material particles were weighed into a 250mL three-necked flask, and 80mL of Tris-HCl buffer solution (10mM, pH 8.5) was added. And mechanically stirring for 1 hour at room temperature until the barium vanadate europium-doped nano material particles are uniformly dispersed in the buffer solution. Then 5mL of template molecule AFB1 with the concentration of 2 mu g/mL is added, and the stirring is continued for 2 hours, so that AFB1 is better contacted with the surface of barium vanadate europium-doped nano material particles. Subsequently, 100mg of dopamine hydrochloride was added and the reaction was continued with stirring for 4 h. Finally, the solid product is separated from the solution under the action of the external magnet. The product was washed with ultrapure water 5 times in sequence to remove unreacted dopamine, 6% acetic acid-60% methanol solution (v/v) until AFB1 was not detected by liquid chromatography, and 5 times with ultrapure water to make the solution neutral. Obtained AFB1-Ba3V2O8And (Eu) @ PDA magnetic molecularly imprinted material is dried for 6h in vacuum at 60 ℃.
Establishing a correlation model for the near infrared spectrum result and the liquid chromatography result:
the establishment of a representative alfalfa forage grass AFB1 extraction process: weighing 10mg of AFB1-Ba3V2O8(Eu) @ PDA magnetic molecularly imprinted material in 100mL beakers, 20mL of a representative alfalfa forage solution was added, respectively, and pH was adjusted to 7.5 with 0.1M NaOH. After ultrasonic extraction is carried out for 5min at room temperature, the molecular imprinting material is quickly separated from the solution under the action of an external magnetic field.
The method is combined with the magnetic nanoparticle near infrared spectrum of the alfalfa sample AFB1Establishing a set process: directly collecting AFB1-Ba adsorbed and enriched with AFB13V2O8(Eu) @ PDA magnetic molecularly imprinted material near infrared diffuse reflection spectrum signal. Selecting an absorption mode to collect a sample diffuse reflection spectrum, wherein the spectrum scanning range is 10000-4000cm-1Resolution of 16cm-1The number of scans was 32, and the average spectrum was calculated by repeating the scan 3 times.
Establishing the determination process of the ultra-high performance liquid chromatography after the desorption of the magnetic nanoparticles of the alfalfa sample AFB 1: 2mL of methanol is taken as a desorbent twice (1mL +1mL) to respectively desorb the AFB1 from the magnetic molecular imprinting material. 0.16mL of the desorption solution was aspirated into a 1.5mL sample bottle, and 0.68mL of water and 0.16mL of acetonitrile were added thereto and mixed well. 10 μ L of the above solution was directly subjected to HPLC, and quantitatively analyzed by a fluorescence detector.
And fourthly, establishing a near-infrared quantitative model of the alfalfa sample AFB1 by utilizing the HPLC detection result and the near-infrared diffuse reflection spectrum result.
Optimization of extraction conditions of the magnetic molecularly imprinted nanoparticles:
1. pH of the sample solution: taking 20ml of alfalfa forage grass solution respectively, adjusting the pH to 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 respectively, and uniformly adding 15mg of AFB1-Ba prepared by the method in example 1 into the sample solution respectively3V2O8The ultrasonic extraction of the (Eu) @ PDA magnetic molecular imprinting material is carried out for 5 minutes, the extraction recovery rate of AFB1 is obviously increased along with the continuous increase of the pH value in the solution, and the extraction recovery rate reaches the maximum value of 90.6 percent when the pH value is 7.0. When the solution is in an alkaline state, the extraction recovery of AFB1 is significantly reduced, which may be related to aflatoxin B1 metal neutral compounds. Thus, pH 7.0 is the optimum acidity for the solution.
2. The dosage of the magnetic molecular imprinting material is as follows: taking 20ml of alfalfa forage grass solution respectively, adjusting the pH to 7.0, and adding AFB1-Ba prepared by the method of example 1 respectively3V2O8(Eu) @ PDA magnetic molecularly imprinted material 5mg, 10mg, 15mg, 20mg, 25mg, 30mg, and ultrasonic extracting for 5min when AFB1-Ba3V2O8When the dosage of the (Eu) @ PDA magnetic molecular imprinting material is increased to 15mg, the recovery rate is increased from67.6% increase to 90.1%; as the amount of material used continues to increase, the recovery rapidly drops to 60%. Therefore, 15mg was chosen as the amount of the magnetic molecularly imprinted material.
3. The magnetic molecularly imprinted nanoparticle ultrasonic extraction adsorption time is as follows: taking 20ml of alfalfa forage grass solution respectively, adjusting pH to 7.0, adding 15mg of AFB1-Ba3V2O8The ultrasonic extraction time is set to be 1min, 2min, 5min, 10min, 15min and 20min, when the ultrasonic time is increased to 5min, the extraction recovery rate of AFB1 is increased to 90%, and the recovery rate is not obviously increased along with the increase of time, so that 5min is the optimal ultrasonic extraction adsorption time.
4. Volume of desorption solution: taking 20ml of alfalfa forage grass solution respectively, adjusting pH to 7.0, adding 15mg of AFB1-Ba3V2O8(Eu) @ PDA magnetic molecular imprinting material, ultrasonic extraction time is 5min, methanol is used as a desorption agent, and when the using amount of the methanol is 1ml, 2ml, 3ml, 4ml and 5ml, the recovery rate of AFB1 is not obviously changed, so 2ml of methanol is selected to be used twice (1ml +1ml) as the optimal using amount.
5. Sample volume: and adding 20 mu L of standard solution with the concentration of 100ng/mLAFB1 into alfalfa forage grass solutions with the volumes of 10, 20, 50, 100, 150 and 200mL, and carrying out enrichment and desorption experiments on aflatoxin B1 under optimized experimental conditions. The recovery rate of aflatoxin B1 is higher at lower sample volumes, and gradually decreases as the sample volume gradually increases. Thus 20mL was used as the optimal alfalfa forage sample volume.
Measuring the content of aflatoxin B1 in alfalfa forage grass:
weighing 20ml of alfalfa forage grass solution, and uniformly adding 15mg of AFB1-Ba3V2O8Stirring and ultrasonic extracting and adsorbing the (Eu) @ PDA magnetic molecular imprinting material for 5min, and adding a magnetic field to carry out AFB1-Ba3V2O8Separating the (Eu) @ PDA magnetic molecular engram material from the supernatant, and pouring out the supernatant solution. Scanning the magnetic molecularly imprinted particles adsorbed with the forage ABF1 by using a Fourier transform near-infrared spectrometer, and collecting sample diffuse reflection in a selected absorption modeThe spectral scanning range of the emission spectrum is 10000-4000cm-1Resolution of 16cm-1The number of scans was 32, and the average spectrum was calculated by repeating the scan 3 times. And 120 alfalfa forage grass samples from 5 Tianyou pastures were subjected to aflatoxin B1 measurement in the same manner, and FIG. 2 was prepared, in which x represents the measured value and y represents the predicted value; the forage grass with the measured value of the aflatoxin being more than 10ng/kg is a sample which is stored for 30 days without drying after being sampled by fresh forage grass, R2Representing a coefficient of determination between predicted and measured values, R2And (3) the standard deviation is more than 0.9, the model can be used for better quantitative analysis, RPD represents relative analysis error, RPD is more than 3, the calibration model is successful, SEC represents corrected standard deviation, and SEP represents predicted standard deviation.
TABLE 1 measurement of aflatoxin Bl content in alfalfa forage samples from different pastures sample measurements (ng/kg)
Note: "-" means below the limit of quantitation
TABLE 2 results of quantitative analysis and validation set of aflatoxins B1 in alfalfa forage grass (ng/kg)
Note: the measured value of the aflatoxin is more than 10ng/kg of forage grass, and the forage grass is a sample which is not dried and stored for 30 days after being sampled
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (7)
1. A method for measuring the content of aflatoxin B1 in forage grass is characterized in that:
(1) preparing alfalfa forage grass solutions to be detected of different samples: weighing 5g of alfalfa forage grass samples which are crushed and sieved by a 60-mesh sieve into a centrifuge tube, adding 20mL of mixed solution of methanol and water with the volume ratio of 75:25, performing ultrasonic extraction for 30min, centrifuging for 5min at 10000rpm, and taking supernatant;
(2) preparation of AFB1-Ba3V2O8(Eu) @ PDA magnetic molecularly imprinted material;
(3) adding 5-30mg of magnetic molecularly imprinted nano material into alfalfa forage grass solution to be detected, adjusting the pH value to 2-10, stirring uniformly, performing ultrasonic extraction at room temperature, simultaneously adding a magnetic field to enable the magnetic molecularly imprinted nano material to be layered under the action of the added magnetic field, removing a supernatant, and analyzing the magnetic molecularly imprinted nano material by using near-infrared diffuse reflection spectroscopy;
(4) desorbing aflatoxin B1 from the magnetic molecularly imprinted nanomaterial with methanol, layering under the action of an external magnetic field, collecting supernatant, and absorbing a small amount of desorption solution to determine aflatoxin B1 by ultra-high performance liquid chromatography;
(5) and (3) repeating the steps 1-4 to measure different samples, correlating the near-infrared spectrum value with the chemical value of the ultra-high performance liquid chromatography by using OPUS (optical phase synthetic Aperture System) spectrum software, and establishing a chemometric model between the near-infrared diffuse reflection spectrum result and the ultra-high performance liquid chromatography result by using a partial least square method.
2. The method for determining the content of aflatoxin B1 in a forage as claimed in claim 1, which is characterized in that: the addition amount of the magnetic molecular imprinting nano material is 15mg, the volume of the alfalfa forage grass solution is 20ml, and the maximum allowable amount of the organic solvent is 10% methanol.
3. The method for determining the content of aflatoxin B1 in a forage as claimed in claim 1, which is characterized in that: the ultrasonic extraction time of the magnetic molecularly imprinted nanomaterial in the step 3 on the aflatoxin B1 in the alfalfa forage grass solution is 5 min; in the step 4, 2ml of methanol is used for desorption, and the molecular imprinting material is desorbed twice.
4. The method for determining the content of aflatoxin B1 in the alfalfa forage grass as claimed in claim 1, wherein: the external magnetic field takes a magnet as an external magnetic field source.
5. The method for determining the content of aflatoxin B1 in a forage as claimed in claim 1, which is characterized in that: in the step 3, scanning and adsorbing the magnetic molecular imprinting particles of the alfalfa sample aflatoxin B1 by using a Fourier transform near-infrared spectrometer, selecting an absorption mode to collect a diffuse reflection spectrum, wherein the spectrum scanning range is 10000-4000cm-1Resolution of 16cm-1The number of scans was 32, and each sample was scanned 3 times in a repetition, and the average spectrum was calculated.
6. The method for determining the content of aflatoxin B1 in a forage as claimed in claim 1, which is characterized in that: the detection conditions of the ultra-high performance liquid chromatography in the step 4 comprise that a chromatographic column is a C18 column, and the grain diameter of the carbon octadecyl silane bonded silica gel is 5 mu m; the mobile phase comprises acetonitrile, methanol and 0.1 percent of formic acid aqueous solution by volume concentration, and the volume ratio is 20:30: 50; the excitation wavelength of the fluorescence detector is 360nm, and the emission wavelength is 440 nm.
7. The method for determining the content of aflatoxin B1 in a forage as claimed in claim 1, which is characterized in that: the magnetic molecularly imprinted nano material is prepared by the following method:
synthesis of europium-doped barium vanadate nanoparticles
At room temperature, NaOH/KOH 9 g in total was mixed uniformly in a molar ratio of 51.5: 48.5 and placed in a 25mL Teflon tube with a lid; 0.5mmol of BaCl2And 0.5mmol V2O5After being mixed evenly, trace europium nitrate is addedThe adulterant is poured into a Teflon tube; placing the Teflon tube into an autoclave, sealing, and placing the autoclave into a muffle furnace preheated to 200 ℃ for heat preservation for 13 hours; taking out the autoclave after heat preservation, naturally cooling to room temperature, dissolving the product with deionized water, washing, filtering, collecting and removing hydroxide on the surface of the product, then washing for a plurality of times with deionized water and absolute ethyl alcohol, and finally drying at 60 ℃ to obtain a white barium vanadate europium-doped sample;
synthesis of barium vanadate europium-doped magnetic molecularly imprinted material
Weighing 0.2g of barium vanadate europium-doped nano material particles in a 250mL three-necked bottle, and adding 80mL of Tris-HCl buffer solution; mechanically stirring for 1h at room temperature until the barium vanadate europium-doped nano material particles are uniformly dispersed in the buffer solution; then adding 5mL of template molecule AFB1 with the concentration of 2 mu g/mL and continuing stirring for 2 h; then 100mg of dopamine hydrochloride is added, and the mixture is continuously stirred and reacts for 4 hours; finally, under the action of an external magnet, separating the solid product from the solution; washing the product with ultrapure water in sequence to remove unreacted dopamine and a solution of 6% acetic acid-60% methanol in volume ratio until AFB1 is not detected by liquid chromatography, and washing with ultrapure water until the solution is neutral; finally obtaining AFB1-Ba3V2O8And (Eu) @ PDA magnetic molecularly imprinted material is dried for 6h in vacuum at 60 ℃.
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