CN111965291A - Sample processing method and automatic processing device - Google Patents
Sample processing method and automatic processing device Download PDFInfo
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- CN111965291A CN111965291A CN202010396835.9A CN202010396835A CN111965291A CN 111965291 A CN111965291 A CN 111965291A CN 202010396835 A CN202010396835 A CN 202010396835A CN 111965291 A CN111965291 A CN 111965291A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a sample processing method and an automatic processing device. The processing method comprises the following steps: modifying a ZSM-5 molecular sieve, adding a treating agent and the ZSM-5 molecular sieve into a sample, carrying out ultrasonic extraction, centrifuging and separating supernate. Sample automatic processing apparatus includes box, first arm, second arm, adsorbent storage tank, solvent storage tank, and the first arm of during operation adds treating agent and molecular sieve to the intraductal centrifuging tube, and the rotor that carries the centrifuging tube drops, carries out supersound extraction, centrifugation to solution in the geminate transistors, recycles the second arm and absorbs the supernatant and detect. The sample processing method and the automatic processing device can improve the processing efficiency, complete the automation of the whole sample processing process and improve the accuracy and the safety of operation.
Description
Technical Field
The invention relates to a sample treatment method and a treatment device, in particular to a treatment method and an automatic treatment device for a pesticide residue sample.
Background
Modern agricultural production increasingly depends on exogenous substances such as pesticides, antibiotics and hormones, and unreasonable use of the substances can generally cause the pesticide residue in agricultural products to exceed the standard, thereby affecting the edible safety. Therefore, the agricultural products are detected by relevant institutions and departments when being harvested and before being sold.
Chromatography is one of the common methods for detecting pesticide residues, and is mainly used for separating and detecting substances according to different partition coefficients of different substances in a stationary phase and a mobile phase. Due to the precision of the instrument, the sample must be processed for the above chromatographic detection. Common sample processing technologies include solid-phase extraction, microwave extraction, gel chromatography and the like, and the methods have the disadvantages of low automation degree, low extraction and purification efficiency, low speed and serious environmental pollution. The matrix dispersion solid phase extraction technology concentrates the traditional sample pretreatment technology, is suitable for extraction and purification of various molecular structures and polar pesticide residues, has small difference of purification effects under the condition of different matrixes, but has poor automation degree and difficult batch treatment because the extracted sample and the extracted material need to be ground in the operation process. In addition, in the conventional sample pretreatment operation, the organic solvent escapes due to repeated addition of the solution for extraction, which is harmful to the health of operators and also affects the detection result.
Disclosure of Invention
The invention aims to provide an automatic sample processing device and a processing method, which can complete the automation of the whole sample processing process and improve the processing efficiency and accuracy.
The sample processing method comprises the following steps:
1) modifying a ZSM-5 molecular sieve: selecting mesoporous molecular sieve ZSM-5 with the silica-alumina ratio of 30 and the aperture of 20-30 nm, taking methylbenzene as a solvent, slowly adding aminopropyltriethoxysilane, stirring, heating and refluxing for 12 hours at 70 ℃, filtering, washing, vacuum drying at 150 ℃, adding 2wt% of a binder, and forming into a 2mm granular structure;
2) adding modified ZSM-5 and a treating agent into the sample to be treated after wall breaking;
3) performing ultrasonic extraction at 60kHz for 10min in a water bath at 40 ℃, adding the treating agent into the centrifuge tube again, and performing ultrasonic extraction at 60kHz for 1 min;
4) centrifuging at 3000rpm for 2min, and sucking the supernatant liquid to another centrifuge tube for later use.
Wherein the binder is chitosan.
The treating agent is ethyl acetate.
Further, the modified ZSM-5 was used in an amount of 2 g.
Further, the amounts of the treatment agents added in the two preceding and subsequent times were 2mL and 3mL, respectively.
In addition, the centrifuge tube used in the centrifugation is covered with a tetrafluoroethylene centrifuge tube cover with a "+" hole in the center.
The invention relates to an automatic sample processing device which comprises a box body (1), a first mechanical arm (2), a second mechanical arm (3), an adsorbent storage tank (4), a hose (5), a centrifugal tube plate (6), a solvent storage tank (7) and a rotor (8).
And a centrifugal machine rotor (8) is arranged on a central axis in the box body (1).
The circle center of the centrifugal tube plate (6) is fixed on the shaft of the centrifugal machine rotor (8), and a plurality of grooves for placing the centrifugal tube are formed in the centrifugal tube plate.
The hose (5) is connected between the interior of the solvent storage tank (7), the first sample inlet (21), the sampling port of the second mechanical arm (3) and the sample collecting pipe.
The first mechanical arm (2) is fixed at the top of the box body (1), and is provided with a first sample inlet (21) for transferring a treating agent and a second sample inlet (22) for transferring a molecular sieve. The sample outlet of the first mechanical arm (2) is arranged right above the centrifugal tube groove, the first mechanical arm (2) moves downwards to the tube opening of the centrifugal tube when the treating agent and the molecular sieve are added, and the first mechanical arm (2) moves upwards to return to the original position after the sample addition is finished.
The sampling port of the second mechanical arm (3) is fixed right above the centrifugal pipe groove, the second mechanical arm (3) moves down to the liquid level of the sample when the sample is sucked, and moves up after the sucking is finished and returns to the original position.
The adsorbent storage tank (4) is arranged at the top of the box body (1), and a sample outlet of the adsorbent storage tank (4) is connected to the second sample inlet (22).
The centrifuge rotor (8) can move up and down along the rotating shaft, the centrifuge tube moves down along with the rotor (8) during ultrasonic extraction, is immersed in water, moves up after extraction is finished, and returns to the original position.
The invention has the following beneficial effects: 1) the method has the advantages of realizing full-automatic sample matrix dispersion solid-phase extraction, having less solvent consumption and good purification effect, and achieving good purification effect; 2) the ZSM-5 molecular sieve has the characteristics of large specific surface area, developed pores and capability of adsorbing macromolecular substances of pesticide residue co-extracted substances, and can remove organic acid, pigments and saccharide impurities of the co-extracted substances more efficiently after modification. 3) The full-automatic sample processing and loading is realized, and the sample extraction efficiency, the parallelism, the precision and the accuracy are improved; 4) the automation degree is high, the sealing performance is high, and the volatilization range of the organic solvent exposed by operators is avoided; 5) the structure of the formed ZSM-5 molecular sieve is convenient for mechanical addition, is beneficial to the separation of extraction solution, and reduces the influence of incomplete separation of purification materials on instruments.
Drawings
FIG. 1 is a flow chart of a sample processing method.
FIG. 2 is a schematic diagram of an automatic sample processing apparatus.
Detailed Description
The automatic sample processing device shown in fig. 2 comprises a box body 1, a first mechanical arm 2, a second mechanical arm 3, an adsorbent storage tank 4, a hose 5, a centrifugal tube plate 6, a solvent storage tank 7 and a rotor 8.
Set up rotor 8 on the inside central axis of box 1, the rotor 8 outside sets up the rail, prevents that the supersound from using water to influence centrifugal operation.
The centre of a circle of the centrifugal tube plate 6 is fixed on the shaft of the centrifugal machine rotor 8, and a plurality of slots for placing the centrifugal tubes are arranged on the centrifugal tube plate.
The flexible pipe 5 is connected between the interior of the solvent storage tank 7 and the first sample inlet 21, and between the sampling port of the second mechanical arm 3 and the sample collecting pipe, and is used for transferring the treating agent or the supernatant in the centrifugal pipe.
The first mechanical arm 2 is fixed on the top of the box body 1, and is provided with a first sample inlet 21 for transferring a treating agent and a second sample inlet 22 for transferring a molecular sieve. The sample outlet of the first mechanical arm 2 is fixed right above the centrifugal tube groove, the first mechanical arm 2 moves downwards to the tube opening of the centrifugal tube when the treating agent and the molecular sieve are added, and the first mechanical arm 2 moves upwards after the sample addition is finished and returns to the original position.
The sampling port of the second mechanical arm 3 is arranged right above the centrifugal pipe groove, the second mechanical arm 3 moves downwards to the liquid level of the sample when the sample is sucked, and moves upwards after the suction is finished to return to the original position.
The adsorbent storage tank 4 is fixed in 1 top of box, and 4 exit ports of adsorbent storage tank and second introduction port 22 fixed connection, the first arm 2 of during operation descend to the centrifugal tube mouth, and the adsorbent gets into in the centrifuging tube through the second introduction port.
The rotor 8 can move up and down along the rotating shaft, the centrifugal tube moves down along with the rotor 8 during ultrasonic extraction, is immersed in water, moves up after extraction is finished, and returns to the original position.
The sample treatment shown in fig. 1 was carried out using the apparatus of the present invention, comprising the following steps:
1) modifying a ZSM-5 molecular sieve: selecting mesoporous molecular sieve ZSM-5 with the silica-alumina ratio of 30 and the aperture of 20-30 nm, taking methylbenzene as a solvent, slowly adding aminopropyltriethoxysilane, stirring, heating and refluxing for 12 hours at 70 ℃, filtering, washing, vacuum drying at 150 ℃ to obtain modified ZSM-5, and adding 2wt% of chitosan as a binder to form the modified ZSM-5 into a 2mm granular structure.
2) 2g of the wall-broken sample to be treated is put into a 10mL centrifuge tube, and a tetrafluoroethylene centrifuge tube cover with a + hole in the center is covered and placed on a centrifuge tube plate 6.
3) The first mechanical arm 2 is operated to add 2g of modified ZSM-5 and 2mL of ethyl acetate into the centrifuge tube, and ultrasonic extraction is carried out for 10min at 60kHz in a water bath at 40 ℃, 3mL of ethyl acetate is added into the centrifuge tube, and ultrasonic extraction is carried out for 1min at 60 kHz.
4) Centrifuging at 3000rpm for 2min, operating the second mechanical arm 3 to suck the upper layer liquid to another centrifuge tube, and detecting.
Claims (8)
1. A method of sample processing, comprising the steps of:
1) modifying a ZSM-5 molecular sieve: selecting mesoporous molecular sieve ZSM-5 with the silica-alumina ratio of 30 and the aperture of 20-30 nm, taking methylbenzene as a solvent, slowly adding aminopropyltriethoxysilane, stirring, heating and refluxing for 12 hours at 70 ℃, filtering, washing, vacuum drying at 150 ℃, adding 2wt% of a binder, and forming into a 2mm granular structure;
2) adding modified ZSM-5 and a treating agent into the sample to be treated after wall breaking;
3) performing ultrasonic extraction at 60kHz for 10min in a water bath at 40 ℃, adding the treating agent into the centrifuge tube again, and performing ultrasonic extraction at 60kHz for 1 min;
4) after centrifuging at 3000rpm for 2min, sucking the supernatant liquid to another centrifuge tube for later use.
2. The method of claim 1, wherein the binding agent is chitosan.
3. The method of claim 1, wherein the treatment agent is ethyl acetate.
4. The method of claim 1, wherein the modified ZSM-5 is used in an amount of 2 g.
5. The method of claim 1, wherein the amounts of the treatment agent used in the two preceding and following treatments are 2mL and 3mL, respectively.
6. The method of claim 1, wherein the centrifuge tube is capped with a tetrafluoroethylene centrifuge tube cap having a "+" hole in the center.
7. The utility model provides a sample automatic processing apparatus, includes that an inside has centrifugation, the box (1) of supersound device, set up centrifuge rotor (8) on the central axis of box (1) inside, characterized by still includes:
the centrifugal tube plate (6) is used for fixing a centrifugal tube, the circle center of the centrifugal tube plate (6) is fixed on the shaft of the rotor (8), and a plurality of grooves for placing the centrifugal tube are formed in the centrifugal tube plate;
the hoses (5) are used for transferring the solution, and the hoses (5) are connected between the interior of the solvent storage tank (7) and the first sample inlet (21) and between the sampling port of the second mechanical arm (3) and the sample collecting pipe;
the first mechanical arm (2) is used for adding a treating agent and a molecular sieve, the first mechanical arm (2) is fixed at the top of the box body (1), a sample outlet of the first mechanical arm (2) is arranged right above the centrifugal tube groove, the first mechanical arm (2) moves downwards to the tube opening of the centrifugal tube when the treating agent and the molecular sieve are added, and the first mechanical arm (2) moves upwards after the sample addition is finished and returns to the original position;
the second mechanical arm (3) is used for sucking the solution, the second mechanical arm (3) is fixed at the top of the box body (1), a sampling port of the second mechanical arm (3) is fixed above the centrifugal pipe groove, the second mechanical arm (3) moves downwards to the liquid level of the sample when the sample is sucked, and moves upwards to return to the original position after the sucking is finished;
the adsorbent storage tank (4) is used for storing an adsorbent, the adsorbent storage tank (4) is arranged at the top of the box body (1), and a sample outlet of the adsorbent storage tank (4) is fixedly connected with the second sample inlet (22).
8. The automatic sample processing device according to claim 7, wherein the rotor (8) can move up and down along the rotation axis, the centrifuge tube moves down along with the rotor (8) during the ultrasonic extraction, is immersed in water, and moves up after the extraction is finished, and returns to the original position.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010396835.9A CN111965291B (en) | 2020-05-12 | 2020-05-12 | Pesticide residue sample treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010396835.9A CN111965291B (en) | 2020-05-12 | 2020-05-12 | Pesticide residue sample treatment method |
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| Publication Number | Publication Date |
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| CN111965291A true CN111965291A (en) | 2020-11-20 |
| CN111965291B CN111965291B (en) | 2022-06-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010396835.9A Active CN111965291B (en) | 2020-05-12 | 2020-05-12 | Pesticide residue sample treatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908588A (en) * | 2021-09-23 | 2022-01-11 | 深圳逗点生物技术有限公司 | Full-automatic solid phase extraction instrument |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908588A (en) * | 2021-09-23 | 2022-01-11 | 深圳逗点生物技术有限公司 | Full-automatic solid phase extraction instrument |
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