CN115468945A - Rapid pesticide detection system for water body and analysis method thereof - Google Patents

Rapid pesticide detection system for water body and analysis method thereof Download PDF

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Publication number
CN115468945A
CN115468945A CN202211189337.2A CN202211189337A CN115468945A CN 115468945 A CN115468945 A CN 115468945A CN 202211189337 A CN202211189337 A CN 202211189337A CN 115468945 A CN115468945 A CN 115468945A
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water
sample
detected
mixing
loading container
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李丹
宋梦翔
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples

Abstract

The invention relates to the technical field of organophosphorus pesticide detection, in particular to a rapid pesticide detection system for a water body and an analysis method thereof, wherein the system comprises a microfluidic module, a water sample input module and a Raman spectrum analysis module; the micro-fluidic module synthesizes the water phase and the oil phase into a composite precious metal nano microgel material and transfers the composite precious metal nano microgel material to the Raman spectrometer module, the water sample input module transfers a water sample to be detected to the Raman spectrometer module, the Raman spectrometer module uniformly mixes the water sample to be detected and the composite precious metal nano microgel material to form a sample to be detected, a Raman spectrum of the sample to be detected is collected, and the detected water sample to be detected flows into a waste liquid recovery container. Compared with the prior art, the micro-fluidic module and the Raman spectrum analysis module are combined, so that the pretreatment process of a complex sample can be reduced or simplified, the rapid analysis and detection of various organophosphorus pesticides in a water sample can be realized, and the stability and the accuracy of an analysis result are ensured.

Description

Rapid pesticide detection system for water body and analysis method thereof
Technical Field
The invention relates to the technical field of organophosphorus pesticide detection, in particular to a rapid pesticide detection system for a water body and an analysis method thereof.
Background
With the growing population and the increasing frequency of natural disasters, it has become necessary to increase the yield of agricultural products. In order to prevent pests (such as fungi, insects, rodents and weeds) from affecting agricultural products, various agricultural chemicals have been widely used worldwide since the first agricultural chemical was synthesized in 1974. Among them, organophosphorus pesticides leave toxic residues in organisms, water and soil, which have caused serious pollution to the environment and ecosystem, due to their low bioaccumulation, rapid biodegradation and wide range of action. Therefore, a sensitive and convenient detection method is needed to quickly and reliably detect the organophosphorus pesticide, and the establishment of the sample injection analysis device and method for quickly detecting the pesticide in the water body on line has important practical significance.
The existing analysis methods commonly used for rapidly detecting the pesticide in the water body are a colorimetric method, capillary Electrophoresis (CE), thin-layer chromatography (TLC), gas-liquid chromatography (GLC), high Performance Liquid Chromatography (HPLC), nuclear Magnetic Resonance (NMR) spectroscopy, mass Spectrometry (MS) and enzyme-linked immunosorbent assay (ELISA), and the above instruments are expensive, long in time consumption, require trained personnel, are not suitable for in-situ online monitoring, and influence the on-site rapid and accurate analysis of the pesticide in the water body to a certain extent.
Disclosure of Invention
In order to solve the above problems, the present invention provides a rapid pesticide detection system for a water body and an analysis method thereof. The system comprises a microfluidic module, a water sample input module and a Raman spectrum analysis module; the micro-fluidic module synthesizes the water phase and the oil phase into a composite precious metal nano microgel material and transfers the composite precious metal nano microgel material to the Raman spectrometer module, the water sample input module transfers a water sample to be detected to the Raman spectrometer module, the Raman spectrometer module uniformly mixes the water sample to be detected and the composite precious metal nano microgel material to form a sample to be detected, a Raman spectrum of the sample to be detected is collected, and the detected water sample to be detected flows into a waste liquid recovery container. Compared with the prior art, the micro-fluidic module and the Raman spectrum analysis module are combined, so that the pretreatment process of a complex sample can be reduced or simplified, the rapid analysis and detection of various organophosphorus pesticides in a water sample can be realized, and the stability and the accuracy of an analysis result are ensured.
With the rapid development of the microfluidic technology, components are integrated on a chip through the micro-machining technology, so that the separation and detection of a sample are realized. Meanwhile, due to the characteristics of portability and convenience, the microfluidic technology is suitable for on-site on-line analysis. Surface-Enhanced Raman Scattering (SERS) is a phenomenon that is related to the concentration of Electromagnetic (EM) fields near metal nanostructures. SERS can amplify the Raman signal of the analyte by several orders of magnitude, is suitable for analyzing and detecting trace pesticides, and simultaneously, the Raman spectrum is insensitive to polar substances such as water, so that the Raman spectrum has a good application prospect in the aspect of detecting water pesticides.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a rapid pesticide detection system for a water body, which comprises a microfluidic module, a water sample input module and a Raman spectrum analysis module;
the microfluidic module comprises a water phase loading container, an oil phase loading container and a microfluidic chip; the water sample input module comprises a water sample loading container; the Raman spectrum analysis module comprises a mixing pool, a detection pool, a laser instrument, a Raman spectrometer, a display terminal and a waste liquid recovery container;
the water phase loading container is connected with the micro-fluidic chip and provides a water phase for the micro-fluidic chip; the oil phase loading container is connected with the micro-fluidic chip and provides an oil phase for the micro-fluidic chip;
the micro-fluidic chip is used for synthesizing a composite noble metal nano microgel material by using an oil phase and a water phase, is connected with the mixing tank and provides the composite noble metal nano microgel material for the mixing tank; the water sample loading container is connected with the mixing pool and provides a water sample to be detected for the mixing pool;
the mixed pool is used for uniformly mixing a water sample to be detected and the composite noble metal nano microgel material to form a sample to be detected and is connected with the detection pool, the detection pool is respectively connected with the laser instrument, the Raman spectrometer and the waste liquid recovery container, the laser instrument is connected with the Raman spectrometer, and the Raman spectrometer is connected with the display terminal.
In one embodiment of the invention, the water phase loading container is connected with the microfluidic chip through an injection pump, the oil phase loading container is connected with the microfluidic chip through an advection pump, the water sample loading container is connected with the mixing pool through an injection pump,
the injection pump is internally provided with a first injector and a second injector, the first injector is connected with the water phase loading container and the microfluidic chip, and the second injector is connected with the water sample loading container and the mixing pool.
In one embodiment of the invention, the syringe pump and the axial flow pump are both adjustable flow rate pumps.
In one embodiment of the invention, the microfluidic chip comprises a top cover layer and a bottom main layer;
the top cover layer comprising a first inlet and a second inlet, the bottom main layer comprising cross-connect channels and an outlet;
the first inlet is connected with a first injector, and the second inlet is connected with an oil phase loading container;
the cross connecting channel is used for synthesizing a water phase and an oil phase into the composite noble metal nano microgel material, and the outlet is connected with the mixing tank.
In one embodiment of the invention, a first valve is arranged at the joint of the water sample loading container and the mixing pool; a second valve is arranged at the joint of the mixing tank and the detection tank; and a third valve is arranged at the joint of the detection pool and the waste liquid recovery container.
In one embodiment of the invention, an S-shaped mixing pipe is provided within the mixing tank.
The second purpose of the invention is to provide an analysis method of a pesticide rapid detection system for a water body, which comprises the following steps:
(S1) opening an advection pump to absorb an oil phase in an oil phase loading container, opening an injection pump to absorb a water phase in a water phase loading container through a first injector, respectively injecting the oil phase and the water phase into a microfluidic chip, and outputting a composite noble metal nano microgel material by the microfluidic chip and transferring the composite noble metal nano microgel material to a mixing pool;
(S2) opening an injection pump to suck the water sample to be detected in the water sample loading container through a second injector and conveying the water sample to be detected to a mixing pool;
(S3) injecting the composite noble metal nano microgel material and a water sample to be detected into a mixing tank, mixing uniformly in an S-shaped mixing pipeline to obtain a sample to be detected, opening a second valve after mixing uniformly, inputting the sample to the detection tank, emitting exciting light by a laser instrument to irradiate the sample to be detected, collecting a Raman signal by a Raman spectrometer, analyzing and processing the Raman signal, obtaining an SERS (surface enhanced Raman scattering) spectrum of the sample to be detected at a display terminal as a result, and analyzing and comparing pesticide components contained in the water sample;
and (S4) after the detection is finished, opening a third valve, and enabling the sample to be detected to flow into a waste liquid recovery container.
In one embodiment of the present invention, characterized in that, in the step (S1), the aqueous phase is gnps @ zif-8, and the oil phase is DCM/BAC;
the composite noble metal nano microgel material is GNPs @ ZIF-8 microgel consisting of GNPs @ ZIF-8 and DCM/BAC.
In one embodiment of the invention, the GNPs @ ZIF-8 is made from PVA, gold nanoparticle GNPs solution, CTAB aqueous solution, zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole, potassium persulfate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and distilled water are evenly mixed to prepare the compound;
the DCM/BAC is prepared by mixing dichloromethane and n-butyl acetate.
In one embodiment of the present invention, in the step (S3), the laser emits excitation light with an excitation wavelength of 785nm and an excitation time of 10S.
Compared with the prior art, the invention has the following beneficial effects:
(1) The rapid pesticide detection system for the water body combines the micro-fluidic technology and SERS detection, and controls the operation, treatment and control of the water phase and the oil phase on a micro scale through the micro-fluidic chip, so that the pretreatment process of a complex sample can be reduced or simplified, the rapid online detection of the pesticide in the water body can be better realized, and the stability and the accuracy of an analysis result are ensured.
(2) According to the invention, the composite noble metal nano microgel material is synthesized in situ, GNPs @ ZIF-8 microgel captures water body pesticide molecules in a mixing pool, and in-situ online detection is carried out in a detection pool, so that the detection of trace pesticides in water body can be realized.
(3) The pesticide rapid detection system for the water body has the characteristics of simplicity in operation, rapidness in determination, easiness in realization of automation and the like.
(4) The pesticide rapid detection system for the water body is simple and easy to understand, does not need complex arrangement, and can be suitable for various detection environments.
Drawings
FIG. 1 is a schematic diagram of a rapid pesticide detection system for a body of water in accordance with the present invention;
FIG. 2 is an SEM photograph of Gold Nanoparticles (GNPs) in example 2 of the present invention;
FIG. 3 is a TEM image of the aqueous phase (GNPs @ ZIF-8) in example 2 of the present invention;
FIG. 4 is SERS spectra of GNPs @ ZIF-8 microgel materials for detecting chlorpyrifos with different concentrations, and the marks (pentagram) shown in the SERS spectra are characteristic peaks of the chlorpyrifos;
FIG. 5 is SERS spectra of GNPs @ ZIF-8 microgel materials for detecting methyl parathion with different concentrations, wherein the marks (pentagram) shown in the SERS spectra are characteristic peaks of the methyl parathion;
FIG. 6 is a schematic diagram showing a linear relationship between the concentration of a standard substance of chlorpyrifos and the intensity of a characteristic peak;
FIG. 7 is a diagram showing a linear relationship between the concentration of a standard substance of methyl parathion and the intensity of a characteristic peak;
in the figure: 1. a water sample loading container; 2. an aqueous phase loading vessel; 3. an oil phase loading container; 4. an injection pump; 5. a advection pump; 6. a microfluidic chip; 7. a mixing tank; 8. a detection cell; 9. a laser instrument; 10. a Raman spectrometer; 11. a display terminal; 12. a waste liquid recovery container; 13. a first syringe; 14. a second syringe; 15. a first valve; 16. a second valve; 17. a third valve; 18. a first microchannel; 19. a second microchannel; 20. a third microchannel; 21. a fourth microchannel; 22. a fifth microchannel; 23. a sixth microchannel; 24. a seventh microchannel.
Detailed Description
The invention provides a rapid pesticide detection system for a water body, which comprises a microfluidic module, a water sample input module and a Raman spectrum analysis module, wherein the microfluidic module is used for detecting the pesticide in the water body;
the microfluidic module comprises a water phase loading container, an oil phase loading container and a microfluidic chip; the water sample input module comprises a water sample loading container; the Raman spectrum analysis module comprises a mixing pool, a detection pool, a laser instrument, a Raman spectrometer, a display terminal and a waste liquid recovery container;
the water phase loading container is connected with the micro-fluidic chip and provides a water phase for the micro-fluidic chip; the oil phase loading container is connected with the micro-fluidic chip and provides an oil phase for the micro-fluidic chip;
the micro-fluidic chip is used for synthesizing a composite noble metal nano microgel material by using an oil phase and a water phase, is connected with the mixing tank and provides the composite noble metal nano microgel material for the mixing tank; the water sample loading container is connected with the mixing tank and is used for providing a water sample to be detected for the mixing tank;
the mixed pool is used for uniformly mixing a water sample to be detected and the composite noble metal nano microgel material to form a sample to be detected and is connected with the detection pool, the detection pool is respectively connected with the laser instrument, the Raman spectrometer and the waste liquid recovery container, the laser instrument is connected with the Raman spectrometer, and the Raman spectrometer is connected with the display terminal.
In one embodiment of the invention, the water phase loading container is connected with the microfluidic chip through an injection pump, the oil phase loading container is connected with the microfluidic chip through an advection pump, the water sample loading container is connected with the mixing pool through the injection pump,
the injection pump is internally provided with a first injector and a second injector, the first injector is connected with the water phase loading container and the microfluidic chip, and the second injector is connected with the water sample loading container and the mixing pool.
In one embodiment of the invention, the syringe pump and the axial flow pump are both adjustable flow rate pumps.
In one embodiment of the invention, the microfluidic chip comprises a top cover layer and a bottom main layer;
the top cover layer comprising a first inlet and a second inlet, the bottom main layer comprising cross-connect channels and an outlet;
the first inlet is connected with a first injector, and the second inlet is connected with an oil phase loading container;
the cross connecting channel is used for synthesizing the water phase and the oil phase into the composite precious metal nano microgel material, and the outlet is connected with the mixing pool.
In one embodiment of the invention, a first valve is arranged at the joint of the water sample loading container and the mixing pool; a second valve is arranged at the joint of the mixing tank and the detection tank; and a third valve is arranged at the joint of the detection pool and the waste liquid recovery container.
In one embodiment of the invention, an S-shaped mixing conduit is provided within the mixing tank.
The invention provides an analysis method of a rapid pesticide detection system for a water body, which comprises the following steps:
(S1) opening an advection pump to absorb an oil phase in an oil phase loading container, opening an injection pump to absorb a water phase in a water phase loading container through a first injector, respectively injecting the oil phase and the water phase into a microfluidic chip, and outputting a composite noble metal nano microgel material by the microfluidic chip and transferring the composite noble metal nano microgel material to a mixing pool;
(S2) opening an injection pump to suck the water sample to be detected in the water sample loading container through a second injector and conveying the water sample to be detected to a mixing pool;
(S3) injecting the composite noble metal nano microgel material and a water sample to be detected into a mixing tank, uniformly mixing in an S-shaped mixing pipeline to obtain a sample to be detected, opening a second valve after uniform mixing, inputting the sample to be detected into a detection tank, emitting exciting light by a laser instrument to irradiate the sample to be detected, collecting a Raman signal by a Raman spectrometer, analyzing and processing the Raman signal, obtaining an SERS (surface enhanced Raman scattering) spectrum of the sample to be detected at a display terminal as a result, and analyzing and comparing pesticide components contained in the water sample;
and (S4) after the detection is finished, opening a third valve, and enabling the sample to be detected to flow into a waste liquid recovery container.
In one embodiment of the present invention, characterized in that, in the step (S1), the aqueous phase is gnps @ zif-8, and the oil phase is DCM/BAC;
the composite noble metal nano microgel material is GNPs @ ZIF-8 microgel consisting of GNPs @ ZIF-8 and DCM/BAC.
In one embodiment of the invention, the GNPs @ ZIF-8 is made from PVA, gold nanoparticle GNPs solution, CTAB aqueous solution, zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole, potassium persulfate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and distilled water are uniformly mixed to obtain the compound;
the DCM/BAC is prepared by uniformly mixing dichloromethane and n-butyl acetate.
In one embodiment of the present invention, in the step (S3), the laser emits excitation light with an excitation wavelength of 785nm and an excitation time of 10S.
The invention is described in detail below with reference to the figures and specific embodiments.
In the description of the present invention, unless expressly stated or limited otherwise, the terms "connected," "connected," and "fixed" are to be construed broadly, e.g., as meaning permanently connected, removably connected, or integral to one another; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the present invention, unless expressly stated or limited otherwise, the recitation of a first feature "on" or "under" a second feature may include the recitation of the first and second features being in direct contact, and may also include the recitation that the first and second features are not in direct contact, but are in contact via another feature between them. Also, the first feature "on," "above" and "over" the second feature may include the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
In the description of the present embodiment, the terms "upper", "lower", "left", "right", and the like are based on the orientations and positional relationships shown in the drawings, and are only for convenience of description and simplicity of operation, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used only for descriptive purposes and are not intended to have a special meaning.
In the following examples, all reagents used were commercially available reagents unless otherwise specified; the detection means and the method are conventional detection means and methods in the field.
Example 1
A rapid pesticide detection system for a water body is shown in figure 1 and comprises a microfluidic module, a water sample input module and a Raman spectrum analysis module;
the micro-fluidic module outputs a composite noble metal nano microgel material, fully collides and combines with a water sample to be detected output by the water sample input module to form a sample to be detected, and performs detection and data analysis in the Raman spectrum analysis module;
the microfluidic module comprises a water phase loading container 2, an oil phase loading container 3, an injection pump 4, an advection pump 5 and a microfluidic chip 6;
the water sample input module comprises a water sample loading container 1 and an injection pump 4;
the Raman spectrum analysis module comprises a mixing pool 7, a detection pool 8, a laser instrument 9, a Raman spectrometer 10, a display terminal 11 and a waste liquid recovery container 12;
a first injector 13 and a second injector 14 are arranged in the injection pump 4;
the microfluidic chip 6 comprises a top cover layer and a bottom main layer; the top cover layer comprises a first inlet, a second inlet and a screw hole, and the bottom main layer comprises a cross-connecting channel and an outlet;
the aqueous phase loading vessel 2 is connected to a first injector 13 through a first microchannel 18, the first injector 13 being connected to a first inlet through a second microchannel 19; the oil phase loading container 3 is connected with the advection pump 5 through a third micro-channel 20, the advection pump 5 is connected with a second inlet through a fourth micro-channel 21, a water phase entering from the first inlet and an oil phase entering from the second inlet enter a cross-connection channel through screw holes to synthesize a composite precious metal nano microgel material, and an outlet is connected with the mixing tank 7 through a fifth micro-channel 22;
the water sample loading container 1 is connected with a second injector 14 through a sixth micro-channel 23, the second injector 14 is connected with the mixing pool 7 through a seventh micro-channel 24, and the seventh micro-channel 24 is provided with a first valve 15;
an S-shaped mixing pipeline in the mixing pool 7 uniformly mixes the water sample to be detected with the composite noble metal nano microgel material to form a sample to be detected; and is connected with detection cell 8 through second valve 16, and detection cell 8 connects laser instrument 9, raman spectrometer 10 respectively, laser instrument 9 also is connected with raman spectrometer 10, and detection cell 8 still is connected with waste liquid recovery container 12 through third valve 17.
The injection pump 4 and the parallel flow pump 5 are adjustable flow rate pumps, the flow adjustable ranges are 0.01-10ml/min and 1-100ml/min respectively, and flow setting can be carried out according to requirements;
the laser emission wavelength of the laser instrument 9 can be 532nm, 633nm, 785nm, 1064nm or the like; the display terminal 11 may be a PC or a display.
Example 2
The embodiment provides a preparation method of a composite noble metal nano microgel material, which comprises the following steps:
(1) And (3) synthesis of gold nanoparticle GNPs: 100ml H is added into a three-neck flask 2 O，1mlHAuCl 4 ·3H 2 Heating to boil, quickly injecting 1ml of 1% sodium citrate solution, quickly injecting 1ml of PVP solution after the solution turns to be purple red, then stopping heating, and cooling to room temperature to obtain Gold Nanoparticles (GNPs); gold nanoparticles GNPs centrifugation (8000r, 10min)After two purifications, redispersed in distilled water, sonicated for 30 minutes, and stored at 4 ℃ for further use, GNPs were prepared with morphologies as shown in fig. 2.
(2) Synthesis of the oily phase (DCM/BAC): dichloromethane (DCM) and n-Butyl Acetate (BAC) were mixed at a ratio of 1:1, the total amount is 800mL, 2mL of tetramethylethylenediamine is added, and the mixture is shaken up for standby.
(3) Synthesis of the aqueous phase (GNPs @ ZIF-8): weighing 10g PVA in a clean 50mL beaker, adding 1mL of the gold nanoparticle GNPs solution synthesized in step (1), 0.144mL 1x10 -3 Aqueous M CTAB solution, 1mL 2.4x10 -2 M Zn(NO 3 ) 2 ·6H 2 O,1mL of 1.32M 2-methylimidazole (2-Hmin), weighing 0.16g of potassium persulfate, dissolving the potassium persulfate with 3.5g of distilled water, adding the dissolved potassium persulfate into weighed PVA, adding 3.0g of 2-acrylamide-2-methylpropanesulfonic acid sodium salt, stirring at a proper speed for about 20min, continuously stirring until the color is uniform, removing micro bubbles in the solution by ultrasound to obtain GNPs @ ZIF-8, and continuously stirring for later use to prepare the GNPs @ ZIF-8 with the shape shown in figure 3.
(4) Synthesizing a composite noble metal nano microgel material (GNPs @ ZIF-8 microgel): after pretreatment (TBP 5010S advection pump 5 is turned on, set speed 10mL/min, ethanol is pumped for about 1min to clean system pipeline), third microchannel 20 is connected to oil phase loading container 3, and ethanol is discharged by pumping oil phase and then suspended.
The aqueous phase was pumped into a first syringe 13 (a stainless steel microinjector compatible with the LSP01-1BH high pressure Syringe Pump 4), the first syringe 13 was mounted and fixed in the Syringe Pump 4 at a set speed of 1mL/min.
And simultaneously starting the injection pump 4 and the advection pump 5, setting the speed of the advection pump 5 to be 25mL/min and the speed of the injection pump 4 to be 0.01mL/min after the flow rates of the outlet ends of the water phase and the oil phase are stable, enabling the water phase and the oil phase to enter the micro-fluidic chip 6 through two inlets (a water phase-first inlet and an oil phase-second inlet) of the top covering layer, forming a composite noble metal nano microgel material (GNPs @ ZIF-8 microgel) in the cross connecting channel, and enabling the material to flow out through an outlet.
Example 3
The present embodiment provides an analysis method of a rapid pesticide detection system for a water body, where the system used in the present embodiment is the system described in embodiment 1, and the composite noble metal nano microgel material used in the present embodiment is the composite noble metal nano microgel material prepared in embodiment 2, and specifically includes the following steps:
(1) Opening the injection pump 4 and the first valve 15, closing the second valve 16 at the moment, and uniformly mixing the water sample to be detected conveyed by the seventh microchannel 24 and the composite noble metal nano gel material conveyed by the microfluidic chip 6 in the S-shaped mixing pipeline to obtain a sample to be detected;
(2) Opening the second valve 16, transferring the sample to be detected to the detection cell 8, and then closing the second valve 16 and the third valve 17; the laser instrument 9 emits exciting light and irradiates a sample to be detected (the exciting time is 10 s), the Raman spectrometer 10 collects Raman signals and analyzes and processes the Raman signals, and the detection result is subjected to atlas display on the display terminal 11 through a USB bus, can also be sent wirelessly and is subjected to online monitoring in a network management center; after the detection is finished, the third valve 17 is opened, and the sample to be detected after the detection is finished enters the waste liquid recovery container 12, so that secondary pollution is avoided; when the waste liquid recovery container 12 is full, the two-way ball valve gives an alarm and automatically closes, and then the waste liquid recovery container 12 is replaced;
(3) Preparing chlorpyrifos and methyl parathion standard solutions with different concentrations, detecting spectral signals of the solutions by adopting a portable spectroradiometer and taking GNRs @ ZIF-8 microgel as an SERS substrate, and adopting a Raman spectrum peak of 678cm -1 And 1237cm -1 、1110cm -1 And 1346cm -1 As characteristic peaks for the determination of chlorpyrifos and methyl parathion. The concentration of chlorpyrifos and methyl parathion in the solution to be tested is gradually increased (1.0 multiplied by 10) -7 M～1.0×10 -3 M), 678cm in Raman spectrogram -1 And 1237cm -1 、1110cm -1 And 1346cm -1 The intensity of the characteristic peak at four positions is gradually increased (FIG. 4 and FIG. 5), and 678cm is selected -1 And 1110cm -1 The corresponding peak intensity combined with the linear standard curve (figure 6 and figure 7) can calculate the content of chlorpyrifos and methyl parathion, and the Detection Limit (DL) is measured according to 3 times according to the linear relation between the concentration of chlorpyrifos and methyl parathion and the Raman signal intensityThe ratio of the blank standard deviation (delta) to the linear curve slope (k) is calculated, namely DL =3 delta/k, and the detection limits of chlorpyrifos and methyl parathion are as follows: chlorpyrifos-6 nM, methyl parathion-0.001 nM.
(4) And (3) substituting the Raman signal intensity detected in the step (2) into the standard curve to obtain the concentrations of chlorpyrifos and methyl parathion in the water sample.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A rapid pesticide detection system for a water body is characterized by comprising a microfluidic module, a water sample input module and a Raman spectrum analysis module;
the microfluidic module comprises a water phase loading container, an oil phase loading container and a microfluidic chip; the water sample input module comprises a water sample loading container; the Raman spectrum analysis module comprises a mixing pool, a detection pool, a laser instrument, a Raman spectrometer, a display terminal and a waste liquid recovery container;
the water phase loading container is connected with the micro-fluidic chip and provides a water phase for the micro-fluidic chip; the oil phase loading container is connected with the micro-fluidic chip and provides an oil phase for the micro-fluidic chip;
the micro-fluidic chip is used for synthesizing a composite noble metal nano microgel material by using an oil phase and a water phase, is connected with the mixing tank and provides the composite noble metal nano microgel material for the mixing tank; the water sample loading container is connected with the mixing pool and provides a water sample to be detected for the mixing pool;
the mixed pool is used for uniformly mixing a water sample to be detected and the composite precious metal nano microgel material to form a sample to be detected, and is connected with the detection pool, the detection pool is respectively connected with the laser instrument, the Raman spectrometer and the waste liquid recovery container, the laser instrument is connected with the Raman spectrometer, and the Raman spectrometer is connected with the display terminal.
2. The system for rapidly detecting the pesticide in the water body according to claim 1, wherein the water phase loading container is connected with the micro-fluidic chip through an injection pump, the oil phase loading container is connected with the micro-fluidic chip through an advection pump, the water sample loading container is connected with the mixing pool through an injection pump,
the injection pump is internally provided with a first injector and a second injector, the first injector is connected with the water phase loading container and the microfluidic chip, and the second injector is connected with the water sample loading container and the mixing pool.
3. The system for rapidly detecting pesticide in water body according to claim 2, wherein the injection pump and the flow pump are both adjustable flow rate pumps.
4. The system for rapidly detecting the pesticide in the water body as claimed in claim 3, wherein the microfluidic chip comprises a top covering layer and a bottom main layer;
the top cover layer comprises a first inlet and a second inlet, the bottom main layer comprises cross-connect channels and outlets;
the first inlet is connected with a first injector, and the second inlet is connected with an oil phase loading container;
the cross connecting channel is used for synthesizing a water phase and an oil phase into the composite noble metal nano microgel material, and the outlet is connected with the mixing tank.
5. The system for rapidly detecting the pesticide in the water body according to claim 1, wherein a first valve is arranged at the joint of the water sample loading container and the mixing tank; a second valve is arranged at the joint of the mixing tank and the detection tank; and a third valve is arranged at the joint of the detection pool and the waste liquid recovery container.
6. The system for rapidly detecting pesticide in water body according to claim 1, wherein an S-shaped mixing pipeline is arranged in the mixing tank.
7. An analysis method of the rapid pesticide detection system for water bodies as set forth in any one of claims 1 to 6, characterized by comprising the steps of:
(S1) opening an advection pump to absorb an oil phase in an oil phase loading container, opening an injection pump to absorb a water phase in a water phase loading container through a first injector, respectively injecting the oil phase and the water phase into a microfluidic chip, and outputting a composite noble metal nano microgel material by the microfluidic chip and transferring the composite noble metal nano microgel material to a mixing pool;
(S2) opening an injection pump to suck the water sample to be detected in the water sample loading container through a second injector and conveying the water sample to be detected to a mixing pool;
(S3) injecting the composite noble metal nano microgel material and a water sample to be detected into a mixing tank, mixing uniformly in an S-shaped mixing pipeline to obtain a sample to be detected, opening a second valve after mixing uniformly, inputting the sample to the detection tank, emitting exciting light by a laser instrument to irradiate the sample to be detected, collecting a Raman signal by a Raman spectrometer, analyzing and processing the Raman signal, obtaining an SERS (surface enhanced Raman scattering) spectrum of the sample to be detected at a display terminal as a result, and analyzing and comparing pesticide components contained in the water sample;
and (S4) after the detection is finished, opening a third valve, and enabling the sample to be detected to flow into a waste liquid recovery container.
8. The analytical method for a rapid pesticide detection system for water bodies as claimed in claim 7, wherein in the step (S1), the aqueous phase is GNPs @ ZIF-8, and the oil phase is DCM/BAC;
the composite noble metal nano microgel material is GNPs @ ZIF-8 microgel consisting of GNPs @ ZIF-8 and DCM/BAC.
9. The analysis method of the rapid pesticide detection system for water bodies according to claim 8,characterized in that the GNPs @ ZIF-8 is prepared from PVA, gold nanoparticle GNPs solution, CTAB aqueous solution and Zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole, potassium persulfate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and distilled water are uniformly mixed to obtain the compound;
the DCM/BAC is prepared by uniformly mixing dichloromethane and n-butyl acetate.
10. The analysis method of the rapid pesticide detection system for water bodies as claimed in claim 7, wherein in the step (S3), the excitation wavelength of the excitation light emitted by the laser instrument is 785nm, and the excitation time is 10S.
CN202211189337.2A 2022-09-28 2022-09-28 Rapid pesticide detection system for water body and analysis method thereof Pending CN115468945A (en)

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CN202211189337.2A CN115468945A (en) 2022-09-28 2022-09-28 Rapid pesticide detection system for water body and analysis method thereof

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