CN110231423B - Method for measuring pyrethroid pesticides in grains by dispersion liquid microextraction-high performance liquid chromatography - Google Patents
Method for measuring pyrethroid pesticides in grains by dispersion liquid microextraction-high performance liquid chromatography Download PDFInfo
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Abstract
The invention belongs to the technical field of food chemistry, and provides a method for determining pyrethroid pesticides in grains by using dispersion liquid-liquid microextraction-high performance liquid chromatography. Thymol or choline chloride is used as a hydrogen bond acceptor, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid or capric acid is used as a hydrogen bond donor, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is any one of 1/5,1/4,1/3,1/2,1/1,2/1,3/1 or 4/1; the hydrophobic eutectic solvent synthesized by mixing the hydrogen bond acceptor and the donor is used as an extracting agent to carry out dispersion liquid-liquid microextraction, and the pyrethroid pesticides in the grains are determined by high performance liquid chromatography. The method has the advantages of simple operation, rapidness, sensitivity, small using amount of the extracting agent, easy collection, environmental protection and the like, and can be used for detecting the pyrethroid pesticides in various grain samples. Can avoid using harmful organic solvent, has small using amount of an extracting agent, and has the remarkable advantages of simple and quick operation, easy collection, environmental protection, good reproducibility and the like.
Description
Technical Field
The invention belongs to the technical field of food chemistry, and particularly relates to a method for determining pyrethroid pesticides in grains by using dispersion liquid microextraction-high performance liquid chromatography.
Background
Pyrethroid pesticides are a class of artificially synthesized pesticides simulating natural pyrethrin, are mainly used for preventing and controlling agricultural pests, but are wide in application range, large in quantity and many in contact population, so that poisoning cases frequently occur. Mild cases have headache, nausea, and severe cases have muscle fibrillation, even with coma and impaired renal function. The grain can not only meet the basic requirements of human bodies, but also prevent and treat a plurality of diseases in an auxiliary way, so the quality control of the grain is very important.
The principle of the dispersion liquid-liquid microextraction is that an extractant forms dispersed fine organic liquid drops under the action of a dispersing agent so as to form a water, dispersing agent and extractant emulsion system, and the method is a sample pretreatment method which is simple and rapid, has low cost and high enrichment factor and is concerned by researchers all the time. However, the extractant commonly used in this method is an organic solvent, which is disadvantageous to the operator and the environment. It is therefore particularly important to select a green extractant.
The general technology of the dispersion liquid-liquid microextraction based on suspension solidification is similar to the traditional liquid-liquid dispersion microextraction, the dispersion liquid-liquid microextraction is carried out by adopting an extraction solvent with the melting point close to room temperature and the density smaller than water, and an organic phase is solidified in an ice bath by putting an extraction container after centrifugation, so that the collection of an extract is facilitated, and the collection and the separation can be easily carried out without a special device. The method has the advantages of high speed, good reproducibility, high efficiency, low cost, simple extraction device, low dosage of low-toxicity organic solvent and the like.
Disclosure of Invention
The invention aims to provide a method for determining pyrethroid pesticides in grains by using dispersion liquid-liquid microextraction-high performance liquid chromatography. The method has the advantages of simple operation, rapidness, sensitivity, small using amount of the extracting agent, easy collection, environmental protection and the like, and can be used for detecting the pyrethroid pesticides in various grain samples.
The invention designs and adopts a novel hydrophobic eutectic solvent for the first time, the eutectic solvent is used as an extractant for liquid-liquid microextraction of dispersion liquid, suspension solidification is used for collection, and high performance liquid chromatography is combined to determine and analyze pyrethroid pesticides in grains.
The invention is realized by the following technical scheme: a method for determining pyrethroid pesticides in grain by dispersion liquid microextraction-high performance liquid chromatography comprises the steps of taking thymol or choline chloride as a hydrogen bond acceptor, taking valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid or capric acid as a hydrogen bond donor, wherein the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is any one of 1/5,1/4,1/3,1/2,1/1,2/1,3/1 or 4/1; and (3) mixing a hydrogen bond acceptor and a hydrogen bond donor to synthesize a hydrophobic eutectic solvent serving as an extracting agent, carrying out dispersion liquid-liquid microextraction, and then carrying out high performance liquid chromatography to determine the pyrethroid pesticide in the grain.
The specific determination method comprises the following steps:
(1) preparing a sample solution: accurately weighing 1-5 g of crushed and homogenized grain sample to be detected, accurately weighing the grain sample to be detected to 0.0001 g, adding 0.2-1.2 mL of dispersing agent, carrying out vortex mixing for 3-10 min at a speed of 1000-3500 r/min, and taking out supernatant for later use;
(2) collecting extract liquid: adding 40 mu L-1 mL of hydrophobic eutectic solvent into the supernatant obtained in the step (1), centrifuging for 5-15 min at a speed of 2500-5000 r/min after extraction, then placing in a refrigerator for ice bath for 10-150 min, melting into liquid at room temperature after an extract phase is converted into a solid phase, and sucking by using a glass syringe for collection;
(3) high performance liquid chromatography determination and analysis: and (3) performing sample injection measurement on the prepared standard solution and the solution of the sample to be detected under the set liquid chromatogram condition, and realizing quantitative detection of the pyrethroid pesticide in the sample to be detected according to the chromatogram peak area of the sample to be detected and by combining a standard curve of the concentration of the pyrethroid pesticide corresponding to the chromatogram peak area.
The grain sample to be detected is at least one of corn, wheat, barley, sorghum, rice, oat and rye; the pyrethroid pesticide is any one of bifenthrin, beta-cypermethrin and deltamethrin.
The dispersing agent is any one of methanol, acetonitrile and acetone; the volume of the dispersing agent is 0.4 mL-1.1 mL; the extractant is prepared by mixing thymol and caprylic acid, pelargonic acid or capric acid; the volume of the extracting agent is 40-100 mu L.
The thymol-caprylic acid is mixed as an extracting agent according to the molar ratio of 1/4, and the volume of the extracting agent is 60 mu L. The dispersing agent is acetonitrile, and the volume is 0.8 mL.
The vortex time is 3-8 min; the rotating speed is 1500-3000 r/min.
Centrifuging at 3500-4500 r/min for 7-13 min after extraction in the step (2). The ice-bath time in the refrigerator is 10-40 min.
The specific conditions of the high performance liquid chromatography in the step (3) are as follows: mobile phase A: b is 95% acetonitrile: 5% of water, the flow rate is 0.5 mL/min, the sample injection amount is 20 mu L, and the detection wavelength is 220 nm; before each use, the column was rinsed with mobile phase acetonitrile/water for at least 30 min.
The method adopts the hydrophobic eutectic solvent synthesized by thymol-caprylic acid as the extractant for the first time, and has the remarkable advantages of low cost, simple and quick operation, easy collection, environmental protection, good reproducibility and the like. Since the materials selected by the eutectic solvent are mostly substances existing in nature, most of the eutectic solvent can be biodegraded. Therefore, the eutectic solvent is adopted, the use of harmful organic solvent is avoided, the adverse effect and damage to the ecological environment are reduced, and the method is more green and environment-friendly. Most of the eutectic solvents studied at present are hydrophilic and are easily destroyed in water due to hydrogen bonding. The development of the hydrophobic eutectic solvent greatly widens the application range of the eutectic solvent.
The hydrophobic eutectic solvent has the characteristic of low freezing point, and can be solidified because the freezing point is close to room temperature (10-30 ℃). The eutectic solvent was subjected to ice bath at a certain temperature, suspended in solid phase at the upper end of the test tube and collected. The difficulty of collecting the extract is greatly reduced, the loss is reduced, and the experimental operation is simpler and more convenient. In addition, the use amount of the extracting agent is small, only 60 mu L of the extracting agent is needed, and the dosage of the extracting agent is greatly saved.
The whole experimental process is simple to operate, quick and sensitive, and has the advantages of avoiding using organic solvents, saving the using amount of an extracting agent, being easy to collect, being green and environment-friendly and the like. The recovery rate and precision experiments show that the method is suitable for quality control of the pyrethroid pesticide content in grains.
Drawings
FIG. 1 shows the effect of extractant type on extraction efficiency in the present invention.
FIG. 2 shows the effect of the ratio of the components of the extractant on the extraction efficiency in the present invention.
FIG. 3 is a graph showing the effect of extractant volume on extraction efficiency in the present invention.
FIG. 4 is a graph showing the effect of dispersant volume on extraction efficiency in the present invention.
FIG. 5 shows the effect of the amount of salt added on the extraction efficiency in the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the examples described below, bifenthrin, beta-cypermethrin, deltamethrin standards, sodium chloride, acetonitrile, methanol, thymol, octanoic acid, nonanoic acid, decanoic acid were purchased from Shanghai Alatin Biotech Ltd. Corn, wheat, barley, sorghum, rice, oats, rye are all from Shanxi university of agriculture. Standard stock mixtures of 3 targets were prepared using standards and stored.
Agilent 1260 high performance liquid chromatograph (Agilent); eclipse Plus C18 column (250X 4.6mm, 5 μm); SC-3610 low speed centrifuge (Anhui Zhongkezhongjia instruments, Inc.); electronic balances (ohaus instruments (chang.)); a refrigerator; vortex apparatus.
The method for measuring the pyrethroid pesticides in the grains by dispersion liquid microextraction-high performance liquid chromatography comprises the following specific implementation steps:
(1) preparation of sample solution: accurately weighing 1 g of the crushed and homogenized grain sample to be detected into a 10 mL centrifuge tube, adding 2 mL acetonitrile, performing vortex-assisted extraction for 5 min at a rotation speed of 2500 r/min, and taking out supernatant as a sample solution for a subsequent liquid-liquid microextraction process;
(2) and (3) extraction and collection processes: placing 5 mL of the aqueous solution into a 10 mL centrifuge tube, adding 0.8 mL of the above acetonitrile solution and 60 μ L of a eutectic solvent prepared by mixing thymol-octanoic acid with a molar ratio of 1/4, and mixing well. Then centrifugating for 10 min at 4000 r/min to make the fine liquid drops dispersed in the extraction phase float on the top of the tube. Then, carrying out ice bath on the centrifugal tube for about 10-20 min, after the extract phase is converted into a solid phase, melting the solid phase into liquid at room temperature, sucking the liquid by using a 50 mu L glass syringe, and diluting and injecting the sample by using methanol;
(3) high performance liquid chromatography determination and analysis: and (3) performing sample injection measurement on the prepared standard solution and the solution of the sample to be detected under the set liquid chromatogram condition, and realizing quantitative detection of the pyrethroid pesticide in the sample to be detected according to the chromatogram peak area of the sample to be detected and by combining a standard curve of the concentration of the pyrethroid pesticide corresponding to the chromatogram peak area.
The specific conditions of the high performance liquid chromatography are as follows: the mobile phase was 95% acetonitrile (A) and 5% water (B), the flow rate was 0.5 mL/min, the amount of sample was 20. mu.L, and the detection wavelength was 220 nm. Before each use, the column was rinsed with acetonitrile/water for at least 30 min.
The experimental results are as follows:
linearity and detection limit: the linear curve is obtained by plotting the peak area against the corresponding concentration of the various substances. The method has good linearity for 3 pyrethroids, which is more than 0.9997, and the detection limit is 2.95-4.00 mu g/kg.
Optimizing the extraction process: according to the experimental steps, different extracting agents are adopted for experiments, and the extracting agents are as follows: thymol-octanoic acid, thymol-nonanoic acid, and thymol-decanoic acid (all prepared according to a molar ratio of 1/4). The experimental results are shown in fig. 1, the recovery rates of the three are high, and the extraction efficiency of all analytes is not significantly different. However, the curing time of thymol-nonanoic acid is about 2.5 hours, so that the experimental time is greatly prolonged, and the method is not suitable for practical operation. We chose thymol-octanoic acid as the extractant in two other groups.
Experiments were performed according to the experimental procedure described above using different molar ratios (1/5, 1/4,1/3,1/2,1/1,2/1, 3/1) of the extractant. The results are shown in fig. 2, where different molar ratios of the eutectic solvent have a positive effect on the extraction of the analyte. The obtained eutectic solvent has higher extraction efficiency than other molar ratios when the molar ratio is 1/4. Therefore, the optimal ratio of thymol to caprylic acid is 1/4.
Experiments were performed according to the experimental procedure described above using different volumes (40. mu.L to 100. mu.L) of extractant. As shown in FIG. 3, the enrichment factor of the pyrethroid pesticide is increased and the extraction efficiency is gradually increased as the volume of the eutectic solvent is increased from 40. mu.L to 60. mu.L, and the extraction efficiency tends to be substantially stable as the volume of the eutectic solvent is increased from 60. mu.L to 100. mu.L. It should be noted that when the volume is less than 40 μ L, the volume is too small to be collected and disposed. Therefore, considering the facts and the experimental results, 60 μ L was selected as the volume of the extractant.
Experiments were performed according to the experimental procedure described above using different volumes (0.4 mL to 1.1 mL) of dispersant acetonitrile. As a result, as shown in FIG. 4, the extraction efficiency increased as the volume of acetonitrile was increased from 0.4 mL to 0.8 mL. This is because the dispersion effect becomes better as the volume of the dispersant increases, and the extraction efficiency of the extract increases. However, when the volume of acetonitrile is increased from 0.8 mL to 1.1 mL, the solubility of the analyte in water increases due to the excessive use of the dispersant, and the analyte is not easily extracted, and thus the extraction efficiency decreases. Therefore, 0.8 mL was chosen as the optimal dispersant volume.
Experiments were carried out according to the experimental procedure described above using different amounts (0 g to 1.5 g) of salt. As shown in FIG. 5, the extraction efficiency gradually decreased with the increase in the amount of salt added in the range of 0 g to 1.5 g, and the extraction efficiency reached the highest at 0 g of salt. This result can be explained by the fact that the extraction solvent of thymol-octanoic acid may be destroyed due to hydrogen bonding of chloride ions in solution with hydrogen bond donors, resulting in a decrease in extraction recovery. Therefore, the following experiment was performed without addition of salt.
And (3) actual sample detection: pyrethroid pesticides in 4 grain samples (corn, wheat, barley, oats) were analyzed according to the experimental procedures described above. The extraction concentration is 0.25 mg kg under the optimal condition-1、 2.5 mg kg -1And 25 mg kg-1The three grain sample solutions of (1). All samples were run in triplicate and the recovery calculated using external standard method, the results are shown in table 1.
TABLE 1 recovery of four samples
Claims (8)
1. A method for determining pyrethroid pesticides in grains by dispersion liquid-liquid microextraction-high performance liquid chromatography is characterized by comprising the following steps: thymol or choline chloride is used as a hydrogen bond acceptor, valeric acid, caproic acid, heptanoic acid, caprylic acid or capric acid is used as a hydrogen bond donor, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is any one of 1/5,1/4,1/3,1/2,1/1,2/1,3/1 or 4/1; mixing a hydrogen bond acceptor and a hydrogen bond donor to synthesize a hydrophobic eutectic solvent serving as an extracting agent, carrying out dispersion liquid-liquid microextraction, and then carrying out high performance liquid chromatography to determine the pyrethroid pesticide in the grain;
the specific determination method comprises the following steps:
(1) preparing a sample solution: accurately weighing 1-5 g of crushed and homogenized grain sample to be detected, accurately weighing the grain sample to be detected to 0.0001 g, adding 0.2-1.2 mL of dispersing agent, carrying out vortex mixing for 3-10 min at a speed of 1000-3500 r/min, and taking out supernatant for later use;
(2) collecting extract liquid: adding 40 mu L-1 mL of hydrophobic eutectic solvent into the supernatant obtained in the step (1), centrifuging for 5-15 min at a speed of 2500-5000 r/min after extraction, then placing in a refrigerator for ice bath for 10-150 min, melting into liquid at room temperature after an extract phase is converted into a solid phase, and sucking by using a glass syringe for collection;
(3) high performance liquid chromatography determination and analysis: performing sample injection measurement on the prepared standard solution and the solution of the sample to be detected under a set liquid chromatogram condition, and realizing quantitative detection of the pyrethroid pesticide in the sample to be detected according to the chromatogram peak area of the sample to be detected and by combining a standard curve of the concentration of the pyrethroid pesticide corresponding to the chromatogram peak area;
the specific conditions of the high performance liquid chromatography are as follows: mobile phase A: b is 95% acetonitrile: 5% of water, the flow rate is 0.5 mL/min, the sample injection amount is 20 mu L, and the detection wavelength is 220 nm; before each use, the column was rinsed with mobile phase acetonitrile/water for at least 30 min.
2. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 1, which is characterized in that: the grain sample to be detected is at least one of corn, wheat, barley, sorghum, rice, oat and rye; the pyrethroid pesticide is any one of bifenthrin, beta-cypermethrin and deltamethrin.
3. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 1, which is characterized in that: the dispersing agent is any one of methanol, acetonitrile and acetone; the volume of the dispersing agent is 0.4 mL-1.1 mL; the extractant is prepared by mixing thymol and caprylic acid, pelargonic acid or capric acid; the volume of the extracting agent is 40-100 mu L.
4. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 3, which is characterized in that: the thymol-caprylic acid is mixed as an extracting agent according to the molar ratio of 1/4, and the volume of the extracting agent is 60 mu L.
5. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 4, which is characterized in that: the dispersing agent is acetonitrile, and the volume is 0.8 mL.
6. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 1, which is characterized in that: the vortex time is 3-8 min; the rotating speed is 1500-3000 r/min.
7. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 1, which is characterized in that: centrifuging at 3500-4500 r/min for 7-13 min after extraction in the step (2).
8. The method for determining the pyrethroid pesticide in the grain by the dispersion liquid-liquid microextraction-high performance liquid chromatography as claimed in claim 1, which is characterized in that: the ice-bath time in the refrigerator is 10-40 min.
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