CN113740461B - Method for detecting pesticide residues of eutectic solvent magnetic carbon nanotube dispersed solid phase extraction bactericide - Google Patents
Method for detecting pesticide residues of eutectic solvent magnetic carbon nanotube dispersed solid phase extraction bactericide Download PDFInfo
- Publication number
- CN113740461B CN113740461B CN202111051900.5A CN202111051900A CN113740461B CN 113740461 B CN113740461 B CN 113740461B CN 202111051900 A CN202111051900 A CN 202111051900A CN 113740461 B CN113740461 B CN 113740461B
- Authority
- CN
- China
- Prior art keywords
- magnetic carbon
- des
- carbon nano
- bactericide
- nano tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 53
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 53
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 29
- 230000005496 eutectics Effects 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 18
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 23
- 238000002347 injection Methods 0.000 claims abstract description 20
- 239000007924 injection Substances 0.000 claims abstract description 20
- 238000004458 analytical method Methods 0.000 claims abstract description 15
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 235000015203 fruit juice Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000015197 apple juice Nutrition 0.000 claims description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 2
- 235000019674 grape juice Nutrition 0.000 claims description 2
- 235000013944 peach juice Nutrition 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 4
- HZJKXKUJVSEEFU-UHFFFAOYSA-N 2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)hexanenitrile Chemical compound C=1C=C(Cl)C=CC=1C(CCCC)(C#N)CN1C=NC=N1 HZJKXKUJVSEEFU-UHFFFAOYSA-N 0.000 claims 1
- 239000005944 Chlorpyrifos Substances 0.000 claims 1
- 239000005867 Iprodione Substances 0.000 claims 1
- 239000005800 Kresoxim-methyl Substances 0.000 claims 1
- 239000005811 Myclobutanil Substances 0.000 claims 1
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical group CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims 1
- ONUFESLQCSAYKA-UHFFFAOYSA-N iprodione Chemical compound O=C1N(C(=O)NC(C)C)CC(=O)N1C1=CC(Cl)=CC(Cl)=C1 ONUFESLQCSAYKA-UHFFFAOYSA-N 0.000 claims 1
- ZOTBXTZVPHCKPN-HTXNQAPBSA-N kresoxim-methyl Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1COC1=CC=CC=C1C ZOTBXTZVPHCKPN-HTXNQAPBSA-N 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 claims 1
- 238000004364 calculation method Methods 0.000 abstract description 14
- 238000000605 extraction Methods 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 15
- 229960001231 choline Drugs 0.000 description 15
- 238000000926 separation method Methods 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 10
- VYWQTJWGWLKBQA-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;chloride Chemical compound Cl.NC(N)=O VYWQTJWGWLKBQA-UHFFFAOYSA-N 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- NQCBIMOYRRMVNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrochloride Chemical compound Cl.OCC(O)CO NQCBIMOYRRMVNA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012491 analyte Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OASOQJKCZXXDMI-UHFFFAOYSA-N ethane-1,2-diol;hydrochloride Chemical compound Cl.OCCO OASOQJKCZXXDMI-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for detecting pesticide residues of a eutectic solvent magnetic carbon nano tube dispersion solid phase extraction bactericide, which comprises the following steps of firstly, preparing magnetic carbon nano tubes; step two, preparing a eutectic solvent; step three, preparing DES-methanol solution for later use; step four, preparing the DES magnetic carbon nano tube, and drying for later use; step five, extracting a detection liquid, and carrying out high performance liquid chromatography analysis to sample injection; step six, adding a recovery rate calculation formula:
Description
Technical Field
The invention belongs to the technical field of pesticide detection, and particularly relates to a method for detecting pesticide residues of a eutectic solvent magnetic carbon nano tube dispersion solid phase extraction bactericide.
Background
Various fruit juice beverages are placed on beverage shelves of a supermarket or a community canteen, and in order to increase the yield of raw materials, namely fruits, fruit growers can excessively use bactericide pesticides in the planting process, so that partial pesticides remain on the surfaces of the fruits and even invade the interiors of the fruits, and the pesticides migrate into the fruit juice products to be ingested by human bodies. With the improvement of the living standard of people, the requirements on the quality of diet are increasing, so that the establishment of a safe and effective agricultural product sterilization pesticide residue analysis method is necessary.
The eutectic solvent (DES) is a green environment-friendly solvent, has excellent physical and chemical properties of low vapor pressure, excellent conductivity, simple synthetic route, no toxicity, no harm, no pollution and the like, can replace the conventional organic solvent in the extraction technology, is widely applied to the effective extraction and separation process of polar or nonpolar components, and has low price and easy obtainment of synthetic raw materials. However, the separation process is complex after the eutectic solvent extraction is finished, and the efficiency is low.
In recent years, a separation method based on magnetic materials is widely focused, and researches show that the magnetic modified nano materials are applied to a solid phase extraction technology and have good extraction effect on organic pesticide compounds. The method exposes the magnetic particles in the solution, and makes large-area contact with the target analyte, so that the substances to be detected can be adsorbed from the solution in a short time, and then the substances are separated from the organic solvent under the action of an external magnetic field, thereby saving time, improving experimental efficiency and simplifying the pretreatment process of the experiment. The magnetic nano material and the environment-friendly eutectic solvent are combined to detect the content of the bactericide, so that a safe and effective agricultural product bactericide pesticide residue analysis method is established, and the subsequent separation process is simple and easy to operate.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for detecting the eutectic solvent magnetic carbon nano tube dispersion solid-phase extraction sterilization pesticide residue, which is simple to operate, high in extraction efficiency, environment-friendly and high in sensitivity and accuracy.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the method for detecting the pesticide residue of the eutectic solvent magnetic carbon nano tube dispersion solid phase extraction bactericide comprises the following steps:
weighing 0.2g of carbon nano tube, placing the carbon nano tube into a 250ml conical flask, adding 100ml of deionized water into the conical flask, sealing, performing ultrasonic treatment for 5-20min, weighing 7.4g of soluble ferric salt, adding the conical flask into the conical flask, exhausting air, performing ultrasonic treatment for 5-20min, adding 20ml of ammonia water, exhausting air and sealing into the conical flask, stirring for 1-3h at 50-120 ℃ by using a magnetic stirrer, finally flushing with deionized water, and drying to obtain the magnetic carbon nano tube;
step two, respectively heating by vortex according to the molar ratio of choline chloride to urea, glycol and glycerol of 1:2, 1:2 and 1:1 to obtain a eutectic solvent;
step three, taking the eutectic solvent and the methanol solution prepared in the step two with the volume ratio of 1:2-4, placing the solution into a centrifuge tube, and oscillating until the transparent liquid without layering phenomenon is DES-methanol solution for standby;
step four, the ratio of the DES-methanol solution prepared in the step three to the magnetic carbon nano tube prepared in the step one is 5-20:1, placing the mixed solution in a centrifuge tube, performing ultrasonic treatment in an ultrasonic cleaner for 10-90min, placing the mixed solution in the residual DES-methanol solution prepared in the third step after the first standing for 20-40min, continuing ultrasonic treatment for 10-90min, performing the second standing, washing the DES magnetic carbon nanotubes in the second standing by using the methanol solution, and drying for later use;
respectively adding 5ml deionized water, 200ul bactericide standard sample and DES magnetic carbon nano tube 2-22mg into a centrifuge tube, performing ultrasonic treatment for 10-60min, standing for more than 10min under the action of a magnetic field, removing upper liquid, adding 0.5-4ml of resolving agent, vortex for 1-5min by using a vortex instrument, sucking the upper liquid by using a syringe, injecting into a sample injection bottle through a filter membrane, and performing high performance liquid chromatography analysis to sample injection;
step six, adding a recovery rate calculation formula:
wherein ER-addition recovery;
C S -testing the concentration;
C O -an initial addition concentration in water;
V 0 -a resolving agent;
V S -volume of water sample.
Further, in the first step, the soluble ferric salt is ferric chloride and ferrous chloride, and the molar ratio of the ferric chloride to the ferrous chloride is 1-3:1; the ultrasonic time is 10min; the air in the conical flask is exhausted by adopting a nitrogen air exhaust method; the stirring temperature of the magnetic stirrer is 80 ℃ and the stirring time is 2h.
Further, the eutectic solvent adopted in the second step is one of choline chloride-urea, choline chloride-ethylene glycol and choline chloride-glycerol.
Further, in the third step, the volume ratio of the eutectic solvent to the methanol solution is 1:3.
Further, in the fourth step, the ratio of the DES-methanol solution to the magnetic carbon nano tube is 10-15:1.
Further, in the fourth step, the ultrasonic time in the ultrasonic cleaner is 60min; the first standing time is 30min, and the second standing time is more than 12h; washing the DES magnetic carbon nano tube for 2-3 times by using a methanol solution; the drying temperature was 80 ℃.
Further, in the fifth step, the DES magnetic carbon nanotube is one of a choline chloride-urea DES magnetic carbon nanotube, a choline chloride-ethylene glycol DES magnetic carbon nanotube and a choline chloride-glycerol DES magnetic carbon nanotube.
Further, in the fifth step, the DES magnetic carbon nano tube is 16mg, and the precipitation time is more than 15min; the vortex time is 2.5min; the resolving agent is one of methanol, ethanol and acetonitrile.
Further, in the fifth step, the resolving agent is ethanol, and the dosage of the ethanol is 1ml.
Further, the pore diameter of the filter membrane in the fifth step is between 0.22 and 0.45 um.
Compared with the prior art, the invention adopts the invention, and the technical progress is that:
(1) The method for detecting the bactericide pesticide residue with high sensitivity and accuracy is provided for food safety detection;
(2) The extractant is a magnetic material, is easy to separate under the condition of an externally applied magnetic field, and has simple operation and high extraction efficiency;
(3) The technology uses an environment-friendly eutectic solvent, is environment-friendly, nontoxic and harmless, and does not cause secondary pollution to the environment.
In conclusion, the detection method has the advantages of high sensitivity and accuracy, simplicity in operation, high extraction efficiency and environmental protection; the method is suitable for detecting the sterilizing pesticide residues of agricultural products.
Detailed Description
The following description is made in connection with the preferred embodiments of the present invention. It should be understood that the preferred embodiments described herein are presented for purposes of illustration and explanation only and are not intended to limit the present invention.
The invention provides a method for detecting pesticide residues of a eutectic solvent magnetic carbon nano tube dispersion solid phase extraction bactericide, which comprises the following steps:
weighing 0.2g of carbon nano tube, placing the carbon nano tube into a 250ml conical flask, adding 100ml of deionized water into the conical flask, sealing a bottle mouth by adopting a preservative film, performing ultrasonic treatment for 10min, weighing 5.4g of ferric chloride and 2g of ferrous chloride, adding the ferric chloride into the conical flask, performing nitrogen blowing to remove air, continuing ultrasonic treatment for 10min, adding 20ml of ammonia water into the conical flask, performing nitrogen blowing to remove air, sealing the bottle mouth by adopting the preservative film, stirring for 2h by using a magnetic stirrer at 80 ℃, finally flushing by adopting the deionized water, and placing the mixture into an oven for drying to obtain the magnetic carbon nano tube;
step two, respectively heating by vortex according to the molar ratio of choline chloride to urea, glycol and glycerol of 1:2, 1:2 and 1:1 to obtain a eutectic solvent;
step three, placing 2ml of the eutectic solvent prepared in the step two and 6ml of the methanol solution into a centrifuge tube, and oscillating until the transparent liquid without layering phenomenon is DES-methanol solution for later use;
step four, placing the mixed solution of the DES-methanol solution prepared in the step three and the magnetic carbon nano tube prepared in the step one in a ratio of 5-20:1 into a centrifuge tube, performing ultrasonic treatment in an ultrasonic cleaner for 60min, stopping ultrasonic treatment, standing for 30min for the first time, placing the residual DES-methanol solution prepared in the step three into the ultrasonic cleaner, continuing ultrasonic treatment for 60min, standing for more than 12h for the second time, washing the second standing DES magnetic carbon nano tube with the methanol solution for 2-3 times, and finally drying in an oven at 80 ℃ for later use;
respectively adding 5ml deionized water, 200ul bactericide standard sample and DES magnetic carbon nano tube 2-22mg for 10-60min by ultrasound, standing for more than 15min under the action of a magnetic field, removing upper liquid, adding 0.5-4ml of resolving agent, swirling for 2.5min by a vortex instrument, sucking the upper liquid by a syringe, injecting the upper liquid into a sample injection small bottle through a filter membrane with the aperture of 0.22-0.45um, and carrying out high performance liquid chromatography analysis to sample injection;
step six, adding a recovery rate calculation formula:
wherein ER- -addition recovery rate;
C S -test concentration;
C 0 -initial addition concentration in water;
V 0 -a resolving agent;
V S -the volume of the water sample.
Calibration of the addition recovery calculation equation, adding the analyte mixing standard sample to 5ml water to give an addition concentration of 50ug.L -1 . One of the conditions is changed, and other conditions are not limited, so that the main factors influencing the enrichment efficiency, such as the influence of DES types, the proportion of DES to magnetic nanotubes, the dosage of the DES magnetic nanotubes, the extraction time, the volume of a resolving agent and the like, on the extraction efficiency are optimized.
The magnetic carbon nanotubes in the first step can also be prepared by adopting other prior art.
The ratio of DES-methanol solution to magnetic carbon nanotubes in step four is explained as: a1 ml DES-methanol solution was considered to be 10:1 with 200mg carbon nanotubes.
Example 1
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, respectively adding 2mg magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 10min, precipitating for 15min under the action of an externally applied magnetic field, removing upper liquid, adding 1ml methanol, swirling for 2.5min with a vortex instrument, sucking upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing sample injection high performance liquid chromatography.
Using the addition recovery calculation formula:
wherein ER- -addition recovery rate;
C S -test concentration;
C 0 -initial addition concentration in water;
V 0 -a resolving agent;
V S -the volume of the water sample;
the results are shown in Table 1.
Example 2
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, respectively adding 22mg choline chloride-glycol DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 15min, precipitating under the action of an external magnetic field for 15min, removing upper liquid, adding 4ml ethanol, swirling for 2.5min with a vortex instrument, sucking the upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 3
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, respectively adding 16mg choline chloride-glycol DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 30min, precipitating for 15min under the action of an external magnetic field, removing upper liquid, adding 1ml ethanol, swirling for 2.5min with a vortex instrument, sucking the upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 4
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, respectively adding 16mg choline chloride-glycol DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 60min, precipitating for 15min under the action of an external magnetic field, removing upper liquid, adding 1ml ethanol, swirling for 2.5min with a vortex instrument, sucking the upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 5
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, respectively adding 22mg choline chloride-glycol DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 45min, precipitating under the action of an external magnetic field for 15min, removing upper liquid, adding 1ml ethanol, swirling for 2.5min with a vortex instrument, sucking the upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 6
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, adding 10mg choline chloride-urea DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 30min, precipitating under the action of an external magnetic field for 15min, removing upper liquid, adding 1ml ethanol, swirling for 2.5min with a vortex instrument, taking upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 7
Adding 5m deionized water into a 3-branch separation tube, adding 200ul of bactericide standard sample, adding 10mg of choline chloride-urea DES magnetic carbon nanotube, ultrasonically extracting by an ultrasonic instrument for 30min, precipitating for 15min under the action of an externally applied magnetic field, removing upper liquid, adding 0.5ml of acetonitrile, swirling for 2.5min by a vortex instrument, taking the upper liquid by a syringe, injecting into a sample injection vial by a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 8
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, adding 10mg choline chloride-urea DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 30min, precipitating for 15min under the action of an externally applied magnetic field, removing upper liquid, adding 3ml acetonitrile, swirling for 2.5min with a vortex instrument, taking upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing sample injection high performance liquid chromatography.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 9
Adding 5ml deionized water into a 3-branch separation tube, adding 200ul bactericide standard sample, adding 18mg choline chloride-glycerol DES magnetic carbon nano tube, ultrasonically extracting for 30min by an ultrasonic instrument, precipitating for 15min under the action of an external magnetic field, removing upper liquid, adding 3ml acetonitrile, swirling for 2.5min by a vortex instrument, taking the upper liquid by a syringe, injecting into a sample injection vial by a filter membrane, and performing sample injection high performance liquid chromatography.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Example 10
Adding 5ml deionized water into 3 branch separation tubes, adding 200ul bactericide standard sample, adding 18mg choline chloride-glycerol DES magnetic carbon nanotube, ultrasonically extracting with an ultrasonic instrument for 30min, precipitating under the action of an external magnetic field for 15min, removing upper liquid, adding 1ml ethanol, swirling for 2.5min with a vortex instrument, taking upper liquid with a syringe, injecting into a sample injection vial through a filter membrane, and performing high performance liquid chromatography analysis.
The calculation formula of the addition recovery rate is the same as that of example 1, and the result is shown in Table 1.
Table 1 results of recovery rate of bactericide addition in example 5
Fruit juice sample examples:
and purchasing the sink apple juice and the grape juice from the local supermarket respectively, wherein the American peach juice is lower than the detection limit by the established method. Then, the results of the experiments of the addition recovery rates of 0.1mg/L and 0.5mg/L were carried out on the 3 kinds of juices, respectively, and are shown in Table 2. The recovery rate is 80.2-96.3%, the RSD is 2.4-7.7%, the requirement of pesticide residue analysis can be met, and the method can be applied to detection of actual samples.
Table 2 3 fruit juice 5 germicides 3 concentration addition recovery and RSD
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (3)
1. A method for detecting pesticide residues of a eutectic solvent magnetic carbon nano tube dispersion solid phase extraction bactericide is characterized by comprising the following steps of: the bactericide is chlorpyrifos, myclobutanil, triazolone, kresoxim-methyl and iprodione;
the method for detecting the pesticide residue of the eutectic solvent magnetic carbon nano tube dispersion solid phase extraction bactericide comprises the following steps:
firstly, weighing 0.2g of carbon nano tube, placing the carbon nano tube into a 250ml conical flask, adding 100ml of deionized water into the conical flask, sealing, performing ultrasonic treatment for 10min, weighing 7.4g of soluble ferric salt, adding the soluble ferric salt into the conical flask, discharging air, performing ultrasonic treatment for 10min, wherein the mole ratio of the soluble ferric salt to the ferrous chloride is 1-3:1, adding 20ml of ammonia water, discharging air and sealing into the conical flask, using a nitrogen air discharging method for discharging the discharged air, stirring for 2h by using a magnetic stirrer at 80 ℃, finally washing by using deionized water, and drying to obtain the magnetic carbon nano tube;
step two, heating by vortex with the mol ratio of choline chloride to glycerol being 1:1 to obtain a eutectic solvent;
step three, placing 2ml of the eutectic solvent prepared in the step two and 6ml of the methanol solution into a centrifuge tube, and oscillating until the transparent liquid without layering phenomenon is DES-methanol solution for standby;
step four, the ratio of the DES-methanol solution prepared in the step three to the magnetic carbon nano tube prepared in the step one is 5-20:1, placing the mixed solution in a centrifuge tube, performing ultrasonic treatment in an ultrasonic cleaner for 60min, placing the mixed solution in the residual DES-methanol solution prepared in the third step after the first standing for 30min, continuing ultrasonic treatment for 60min, wherein the second standing time is more than 12h, washing the DES magnetic carbon nano tube in the second standing time for 2-3 times by using the methanol solution, and drying at 80 ℃ for later use;
respectively adding 5ml deionized water, 200 μl bactericide standard sample and DES magnetic carbon nanotube 2-22mg into a centrifuge tube, performing ultrasonic treatment for 10-60min, standing for more than 10min under the action of a magnetic field, removing upper liquid, adding an analytical agent ethanol with the dosage of 1ml, swirling for 2.5min by a vortex instrument, sucking the upper liquid by an injector, injecting into a sample injection bottle through a filter membrane, wherein the aperture of the filter membrane is 0.22 μm, and performing high performance liquid chromatography analysis on sample injection;
the method is used for measuring the sink apple juice, the grape juice and the beautiful juice source peach juice respectively, and the measurement is lower than the detection limit; then 0.1mg/L and 0.5mg/L of the 3 kinds of fruit juice are respectively subjected to an experiment of adding recovery rate, the recovery rate is 80.2-96.3%, the RSD is 2.4-7.7%, the requirement of pesticide residue analysis can be met, and the established method can be applied to detection of actual samples.
2. The method for detecting pesticide residues by using the eutectic solvent magnetic carbon nanotube dispersion solid phase extraction bactericide according to claim 1, which is characterized by comprising the following steps: in the fourth step, the ratio of the DES-methanol solution to the magnetic carbon nano tube is 10-15:1.
3. The method for detecting pesticide residues by using the eutectic solvent magnetic carbon nanotube dispersion solid phase extraction bactericide according to claim 1, which is characterized by comprising the following steps: step five, the DES magnetic carbon nano tube in the step five is 16mg; the sedimentation time is more than 15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111051900.5A CN113740461B (en) | 2021-09-08 | 2021-09-08 | Method for detecting pesticide residues of eutectic solvent magnetic carbon nanotube dispersed solid phase extraction bactericide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111051900.5A CN113740461B (en) | 2021-09-08 | 2021-09-08 | Method for detecting pesticide residues of eutectic solvent magnetic carbon nanotube dispersed solid phase extraction bactericide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113740461A CN113740461A (en) | 2021-12-03 |
| CN113740461B true CN113740461B (en) | 2024-04-09 |
Family
ID=78737272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111051900.5A Active CN113740461B (en) | 2021-09-08 | 2021-09-08 | Method for detecting pesticide residues of eutectic solvent magnetic carbon nanotube dispersed solid phase extraction bactericide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113740461B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117890511A (en) * | 2024-01-12 | 2024-04-16 | 广东柏佳检测科技有限公司 | Pesticide residue detection method for traditional Chinese medicine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106885853A (en) * | 2017-02-14 | 2017-06-23 | 湖北省农业科学院农业质量标准与检测技术研究所 | The quick pre-treating method for determining AVM pesticide residue in edible oil and quantitative analysis method |
| CN109839466A (en) * | 2019-01-24 | 2019-06-04 | 唐玉乐 | A method of testing melamine content in milk powder is detected based on three-dimensional magnetic molecularly imprinted polymer |
| CN110824030A (en) * | 2019-08-27 | 2020-02-21 | 杭州师范大学 | Method for extracting pesticide from curcuma wenyujin |
-
2021
- 2021-09-08 CN CN202111051900.5A patent/CN113740461B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106885853A (en) * | 2017-02-14 | 2017-06-23 | 湖北省农业科学院农业质量标准与检测技术研究所 | The quick pre-treating method for determining AVM pesticide residue in edible oil and quantitative analysis method |
| CN109839466A (en) * | 2019-01-24 | 2019-06-04 | 唐玉乐 | A method of testing melamine content in milk powder is detected based on three-dimensional magnetic molecularly imprinted polymer |
| CN110824030A (en) * | 2019-08-27 | 2020-02-21 | 杭州师范大学 | Method for extracting pesticide from curcuma wenyujin |
Non-Patent Citations (5)
| Title |
|---|
| Deep eutectic solvent magnetic bucky gels in developing dispersive solid phase extraction: Application for ultra trace analysis of organochlorine pesticides by GC-micro ECD using a large-volume injection technique;Seyedeh Mahboobeh Yousefi 等;《Talanta》;20170308;第168卷;第73-81页 * |
| Ultrasound-assisted deep eutectic solvent as green and efficient media combined with functionalized magnetic multi-walled carbon nanotubes as solid-phase extraction to determine pesticide residues in food products;Zhao Jing 等;《Food Chemistry》;20191204;第310卷;第1-8页 * |
| 低共熔溶剂液相微萃取技术测定5种杀菌剂农药残留分析方法;赵桐桐 等;《现代食品科技》;20190831;第35卷(第8期);第281-286页 * |
| 基于低共熔溶剂的萃取分离技术及其应用研究进展;赵泽馨 等;《色谱》;20210228;第39卷(第2期);第152-161页 * |
| 疏水性低共熔溶剂超声辅助分散液液微萃取高效液相色谱法测定环境水中的除草剂残留;赵桐桐 等;《化学试剂》;20201031;第42卷(第10期);第1176-1180页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113740461A (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105214512B (en) | A kind of preparation method and applications of carrier surface graphene oxide membrane | |
| CN113740461B (en) | Method for detecting pesticide residues of eutectic solvent magnetic carbon nanotube dispersed solid phase extraction bactericide | |
| CN112326578B (en) | Method for rapidly detecting histamine in food | |
| CN106645555A (en) | Method for measuring volatile phenol and cyanide in water, soil or municipal sludge | |
| CN101968474A (en) | Method for detecting bisphenol A in drinking water and beverage foods through LC-MS/MS (Liquid Chromatogram-Mass Spectrometry/Mass Spectrometry) | |
| CN106770615A (en) | The method that Sulphur Dioxide in Chinese Herbal Medicines by Iodine Titration Method is remained is determined using ICP MS methods | |
| CN106770116B (en) | The method of Se form in Solid Phase Extraction-AFS DETERMINATION honey and fruit juice | |
| WO2019129294A1 (en) | Security check instrument and method | |
| CN102095727B (en) | Method for carrying out non-destructive qualitative detection on copper | |
| CN110763533B (en) | Pretreatment method suitable for detecting pesticide residues in tobacco through Raman spectrum | |
| CN203044027U (en) | Suction pipe for fast detecting pesticide residue | |
| Li et al. | Simple colorimetric detection of doxycycline and oxytetracycline using unmodified gold nanoparticles | |
| CN105203510B (en) | A kind of microorganism in food rapid detection method | |
| CN107192784A (en) | The detection method of citrinin toxin in a kind of Monas cuspurpureus Went fermentation liquid | |
| CN103969431B (en) | A kind of preparation method of the immunomagnetic beads for hidden state T-2 toxin enrichment purification | |
| CN107748211B (en) | Method for extracting and measuring 5 macamides in maca by using deep eutectic solvent | |
| Lewin et al. | Diffusion denuder assembly for collection and determination of gases in air | |
| CN206114533U (en) | Nitric oxide detect reagent box | |
| CN109142570A (en) | A kind of the cigarette extraction of flavor component and content assaying method in quick-fried pearl | |
| CN101419205B (en) | Method for measuring residual organic solvent in pectins | |
| Bartlet et al. | Determination of arsenic in fruits and vegetables | |
| CN106525670B (en) | The method for measuring nine kinds of halogen acetic acids in air PM2.5 fine particle simultaneously | |
| Wan et al. | A water-soluble membrane for SARS-CoV-2 viral nucleic acid sampling and detection | |
| CN111007177A (en) | Method for detecting benzene series pollutants in air | |
| KR101747039B1 (en) | Method of extracting carotenoid pigment from brown algae using carbon dioxide and co-solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |