CN102778521A - Method for purifying vegetable containing pyrethroid pesticide residue by using graphene - Google Patents
Method for purifying vegetable containing pyrethroid pesticide residue by using graphene Download PDFInfo
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- CN102778521A CN102778521A CN2012101055479A CN201210105547A CN102778521A CN 102778521 A CN102778521 A CN 102778521A CN 2012101055479 A CN2012101055479 A CN 2012101055479A CN 201210105547 A CN201210105547 A CN 201210105547A CN 102778521 A CN102778521 A CN 102778521A
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Abstract
The invention discloses a method for purifying vegetable containing pyrethroid pesticide residue by using grapheme in the field of pesticide residue analysis of vegetables. The method comprises the following steps of (1) extraction, i.e. weighing proper amount of pre-crushed homogenized vegetable sample containing pyrethroid pesticide, adding an extraction solvent into the sample, and performing vortex or vibration extraction; (2) separation, i.e. adding sodium chloride to perform salt precipitation, and performing centrifugal separation; (3) purification, i.e. taking the supernate, adding the grapheme into the supernate, and after the grapheme is fully contacted with the supernate, adding sodium chloride to perform centrifugal separation; and (4) detection, i.e. taking the supernate, adding anhydrous sodium sulfate or magnesium sulfate anhydrous into the supernate, and after the excessive water content is removed, performing gas chromatogram. The grapheme serves as a purifying material, and compared with graphitized carbon black and N-propyl ethylenediamine bonded silica gel which are conventionally used in a laboratory, the grapheme is low in using amount, strong in absorption ability and low in cost; the method is simple, quick and convenient to perform; and the accuracy is high, and the recovery rate is between 96.0 percent and 99.6 percent.
Description
Technical field
The invention belongs to pesticide residue analysis field in the vegetables, be specifically related to a kind ofly utilize Graphene to purify to contain the residual method for vegetable of pyrethrin pesticide.
Background technology
Graphene is a kind of carbonaceous new material of the tightly packed one-tenth individual layer of carbon atom bi-dimensional cellular shape crystalline network; The thickness of this graphite crystal film has only 0.335nm; Be merely 200,000 of hair/, be the elementary cell that makes up other dimension carbonaceous materials (like zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).The theoretical specific surface area of grapheme material is up to 2600m
2/ g has outstanding heat conductivility (3000W/ (mK)) and mechanical property (1060GPa), and at a high speed electron mobility (15000cm under the room temperature
3/ (Vs)).In addition, its special construction makes it have half integral quantum Hall effect, a series of character such as conductivity that never disappear, thereby become the object that scientific circles receive much concern.At present, it is the mechanical property of Graphene that people pay close attention to maximum, good electrical and thermal conductivity performance, but as the material of huge specific surface area, it is fewer that its performance aspect absorption is also reported, and its application aspect pesticide residue analysis more has to be excavated.
Pyrethroid pesticide is the plain chemical constitution of an analoglike natural pyrethrin and synthetic agricultural chemicals is also claimed bionical synthetic pesticide.Have that insecticidal spectrum is wide, drug effect is high,, characteristics such as environment residence time short generally lower to mammal toxicity, also have mite, sterilization and the mould fungus inhibition effect of killing simultaneously.In the kind more than 20 that has of China's use, like fenvalerate, cypermethrin and decis etc.Though pyrethrin pesticide belongs to low-toxin farm chemicals comparatively speaking, it is a neurotoxic substance.Research proof pyrethrin pesticide has plan estrogen active-reproductive endocrine toxicity, all can work the mischief to many-sides such as immunity, cardiovascular systems.Pyrethrin pesticide is sprayed directly on fruit and vegetable surfaces and is absorbed by fruits and vegetables or remain in the surface, can cause that per os poisons, so the residue detection of pyrethroid pesticide is very necessary in the fruits and vegetables.
Agricultural product and food samples component more complicated, residues of pesticides content is extremely low, and pigment content in various vegetables and crops is more, and its existence may influence the life-span of detecting or shortening instrument and chromatographic column.Want to remove pigment and other impurity, reduce the chromatogram Interference Peaks, avoid detecting device and chromatographic column to pollute, the purified treatment of sample is very important.Used purifying adsorbent has Graphon, N-propyl group ethylenediamine bonded silica gel etc. in the pesticide residue analysis, and these adsorbent consumptions are usually at tens milligrams even more, and cost is higher.
Summary of the invention
The object of the present invention is to provide and a kind ofly utilize Graphene to purify to contain the residual method for vegetable of pyrethrin pesticide, the concrete operations step is following:
(1) extraction takes by weighing the vegetable sample that contains pyrethrin pesticide of smashing homogeneous in right amount in advance to pieces, adds to extract solvent vortex or vibration extraction;
(2) separating adding sodium chloride saltouts and centrifuging;
(3) supernatant is got in purification, adds Graphene, and vortex or concussion after making it and getting supernatant fully contacting, add sodium chloride and centrifuging;
(4) detect and to get that supernatant adds anhydrous sodium sulfate or anhydrous magnesium sulfate is removed the laggard capable gas chromatographic detection of excessive moisture.
Pyrethrin pesticide is selected from one or more in the following material described in the step (1): Biphenthrin, Fenpropathrin, lambda-cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis, tetramethrin, allethrin, ether chrysanthemum ester, phenothrin, flucythrinate, taufluvalinate.
Extract solvent described in the step (1) and select a kind of in the following solvent: acetone, acetonitrile, ethyl acetate, methyl alcohol, normal hexane, sherwood oil, methylene chloride.
In the step (3), the different consumption clean-up effect of Graphene is different, for reduce as much as possible impurity to instrument with the influence that detects, the consumption of Graphene is to purify supernatant to colourless being as the criterion.
Said vegetables comprise cucumber, capsicum and spinach etc.
Said Graphene is commercially available.
Beneficial effect of the present invention:
(1) the present invention, compares with Graphon and N-propyl group ethylenediamine bonded silica gel that the laboratory is commonly used as scavenging material with Graphene, and consumption is few, high adsorption capacity, and cost is low; And it is easy and simple to handle quick;
(2) accuracy of the present invention is high, and the recovery is between 96.0%～99.6%.
Description of drawings
Fig. 1 cucumber acetonitrile extract blank does not purify chromatogram;
The interpolation of Fig. 2 cucumber acetonitrile extract does not purify chromatogram;
Fig. 3 cucumber acetonitrile extract adds Graphene and purifies chromatogram.
Embodiment
Following embodiment can make those skilled in the art more comprehensively understand the present invention, but does not limit the present invention in any way.
Embodiment
In smashing the fresh cucumber sample of homogeneous in advance to pieces, add Biphenthrin, Fenpropathrin, lambda-cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis standard solution; Making the interpolation concentration of lambda-cyhalothrin in water is 100 μ g/L; Permethrin is 400 μ g/L; Other are 100 μ g/L, leave standstill 1 hour.Take by weighing above-mentioned sample 5g, add 10mL acetonitrile vortex and extracted in 2 minutes, add 3g sodium chloride and saltout, and 3800 rev/mins of following centrifugings 5 minutes.Get the 5mL supernatant, add suitable amount of graphite alkene vortex 1min and purify; Simultaneously, get acetonitrile extract 2mL, purify with an amount of N-propyl group ethylenediamine bonded silica gel or Graphon.10000 rev/mins were separated in centrifugal 3 minutes, and it is to be detected in the sample introduction bottle to get the 1mL supernatant.Detect with Tianjin, island GC-ECD, chromatographic column is HP-5 (30m * 0.25mm * 0.25 μ m), flow rate of carrier gas: nitrogen 14mL/min; Heating schedule: 120 ℃ keep 1min, rise to 280 ℃ with 25 ℃/min speed then and keep 13min; Injector temperature: 280 ℃; Detector temperature: 300 ℃; Sample introduction pattern: split sampling not; Sample size: 1 μ L.Eight kinds of pyrethrin pesticide appearance times are under this condition: Biphenthrin, 10.268min; Fenpropathrin 10.421min; Lambda-cyhalothrin, 10.993,11.208min; Permethrin, 12.385; Cyfloxylate, 13.382; Cypermethrin, 13.636; Fenvalerate, 15.652,16.144; Decis, 17.026,17.642.The interpolation recovery of 8 kinds of pyrethrin pesticides is followed successively by 97.6%, 98.0%, and 97.5%, 97.7%, 99.6%; 96.2%, 96.0%, 98.1%, relative standard deviation (RSD) is respectively 2.3%; 2.4%, 2.8%, 1.4%, 3.2%; 2.9%, 2.8%, 4.0%, minimum detection limit (LOD) is between the 5 μ g/L-20 μ g/L.The clean-up effect of Graphene can see from the chromatogram of Fig. 1-3 that shown in Fig. 1-3 retention time is that 2.5-5 minute peak obviously weakens after purification; From cucumber acetonitrile extract; The Graphene consumption is followed successively by 0,1.5,3,4.5, can draw among the clean-up effect figure of 6mg, and after the Graphene of 3mg purified the 5ml extract, extract was almost colourless; Capsicum acetonitrile extract; The Graphene consumption is followed successively by 0,1.5,3,4.5, clean-up effect figure and the spinach acetonitrile extract of 6mg, and the Graphene consumption is followed successively by 0,3,9,15, the clean-up effect figure of 18mg shows that Graphene also has good clean-up effect to the pigment in capsicum and the spinach.(cucumber acetonitrile extract from the clean-up effect of Graphon and N-propyl group ethylenediamine bonded silica gel; The Graphon consumption is followed successively by 0,10,20,30, clean-up effect figure and the cucumber acetonitrile extract of 40mg; N-propyl group ethylenediamine bonded silica gel consumption is followed successively by 0,10,20,30,40mg clean-up effect figure) can know; N-propyl group ethylenediamine bonded silica gel is relatively poor to the detergent power of pigment; Graphon will just can make the 2ml extract purify to colourless with 20mg, that is to say that the amount of required Graphon will reach 50mg when purifying the 5ml extract; And the amount of 3mg Graphene just can make it to purify, and the ability of the purification pigment of Graphene is about 17 times of Graphon.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (5)
1. a purification contains the residual method for vegetable of pyrethrin pesticide, it is characterized in that this method is following:
(1) extraction takes by weighing the vegetable sample that contains pyrethrin pesticide of smashing homogeneous in advance to pieces, adds to extract solvent, and vortex or vibration are extracted;
(2) separating adding sodium chloride saltouts and centrifuging;
(3) supernatant is got in purification, adds Graphene, and vortex or concussion after making it and getting supernatant fully contacting, add sodium chloride and centrifuging;
(4) detect and to get that supernatant adds anhydrous sodium sulfate or anhydrous magnesium sulfate is removed the laggard capable gas chromatographic detection of excessive moisture.
2. according to the method described in the claim 1, it is characterized in that: pyrethrin pesticide is selected from one or more in the following material described in the step (1): Biphenthrin, Fenpropathrin, lambda-cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis, tetramethrin, allethrin, ether chrysanthemum ester, phenothrin, flucythrinate, taufluvalinate.
3. according to the method described in the claim 1, it is characterized in that: in the step (3), the consumption of Graphene is to purify supernatant to colourless being as the criterion.
4. according to the method described in the claim 1, it is characterized in that: extract solvent described in the step (1) and select a kind of in the following solvent: acetone, acetonitrile, ethyl acetate, methyl alcohol, normal hexane, sherwood oil, methylene chloride.
5. according to the method described in the claim 1, it is characterized in that: said vegetables comprise cucumber, capsicum and spinach.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104458939A (en) * | 2014-11-26 | 2015-03-25 | 嘉应学院医学院 | Method for detecting camellia nitidissima chi oil type volatile ingredients |
| CN108693003A (en) * | 2018-04-26 | 2018-10-23 | 许昌学院 | A kind of method of leafy vegetable Detecting Pesticide sample pre-treatments |
| CN109283280A (en) * | 2018-11-28 | 2019-01-29 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | A method of rapidly extracting purifies benzoyl urea pesticide residue from water fruits and vegetables |
| CN109668991A (en) * | 2019-03-05 | 2019-04-23 | 河北大学 | A kind of method of Organochlorine Pesticide Residues in ultrasonic wave auxiliary measuring vegetables |
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| CN102121928A (en) * | 2010-12-20 | 2011-07-13 | 天津市农业科学院中心实验室 | Method for processing onion sample containing several pesticide residues before determination |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104458939A (en) * | 2014-11-26 | 2015-03-25 | 嘉应学院医学院 | Method for detecting camellia nitidissima chi oil type volatile ingredients |
| CN104458939B (en) * | 2014-11-26 | 2016-05-18 | 嘉应学院医学院 | A kind of Camellia nitidissima oils volatile ingredient detection method |
| CN108693003A (en) * | 2018-04-26 | 2018-10-23 | 许昌学院 | A kind of method of leafy vegetable Detecting Pesticide sample pre-treatments |
| CN109283280A (en) * | 2018-11-28 | 2019-01-29 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | A method of rapidly extracting purifies benzoyl urea pesticide residue from water fruits and vegetables |
| CN109283280B (en) * | 2018-11-28 | 2021-07-13 | 广西壮族自治区农业科学院 | Method for rapidly extracting and purifying benzoyl urea pesticide residues from fruits and vegetables |
| CN109668991A (en) * | 2019-03-05 | 2019-04-23 | 河北大学 | A kind of method of Organochlorine Pesticide Residues in ultrasonic wave auxiliary measuring vegetables |
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| CN102778521B (en) | 2014-04-16 |
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