CN109827948B - Quick detection method of dithiocarbamate pesticides - Google Patents
Quick detection method of dithiocarbamate pesticides Download PDFInfo
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- CN109827948B CN109827948B CN201910214552.5A CN201910214552A CN109827948B CN 109827948 B CN109827948 B CN 109827948B CN 201910214552 A CN201910214552 A CN 201910214552A CN 109827948 B CN109827948 B CN 109827948B
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- dithiocarbamate
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- 239000012990 dithiocarbamate Substances 0.000 title claims abstract description 39
- 239000000575 pesticide Substances 0.000 title claims abstract description 39
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- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
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Images
Abstract
The invention discloses a method for detecting dithiocarbamate pesticides in agricultural products, which comprises the following steps: 1) mixing an agricultural product to be detected with an organic solvent, a first salt bag and a second salt bag, so that the dithiocarbamate pesticide enters the organic solvent, and extracting, filtering or centrifuging to obtain a clear liquid detection sample, wherein the first salt bag is used for destroying the cell structure of the agricultural product, and the second salt bag is used for absorbing water in the agricultural product; 2) immersing the active area of the SERS substrate in a liquid detection sample for a preset time to enable dithiocarbamate pesticide molecules to be adsorbed or grabbed to the surface of the SERS substrate; 3) drying the SERS substrate obtained in the step (2) and then carrying out Raman detection; the invention has the advantages of simple operation and low cost on the premise of high detection accuracy, high detection sensitivity and low detection lower limit.
Description
Technical Field
The invention belongs to the technical field of pesticide detection, particularly relates to a rapid detection method of dithiocarbamate pesticides, and particularly relates to detection of dithiocarbamate pesticides contained in fruits, vegetables and crops.
Background
The dithiocarbamate pesticide is an insecticide widely applied to crops, and can interact with enzymes containing sulfhydryl (-SH) and coenzyme of fungus cells to achieve the purpose of killing insects. Despite the low toxicity of the compound, the application of the compound in fruits and vegetables still has potential environmental pollution problems and influences on human health, for example, the compound can stimulate human skin and mucous membranes, and the derivative products thereof have the possibility of causing carcinogenesis and human body deformity, so that the dithiocarbamate pesticides remained in crops are detected at present to judge whether the pesticide meets the national or international standard.
The prior art method for detecting dithiocarbamate pesticides comprises the following steps: colorimetry, high performance liquid chromatography, and the like;
for example, headspace sample injection-gas chromatography (for example, detection of dithiocarbamate pesticide residues in imported and exported fruits SN/T0157-1992) and ultraviolet spectrocolorimetry (for example, research on a method for rapidly detecting dithiocarbamate pesticide residues in agricultural products such as tea leaves and the like of Wang Jiaying, Wang Danhong and the like of food science institute of Fujian agriculture and forestry university), however, instruments required by the gas chromatography are expensive, the ultraviolet spectrocolorimetry is based on the principle that dithiocarbamate pesticides are decomposed into carbon disulfide, qualitative and quantitative analysis is performed through reaction of the carbon disulfide and a color developing agent, but false positives appear in the actual detection process, and in addition, color is brought into a receiving tube during pretreatment of some foods with deep color, and normal analysis is interfered.
For another example, chinese invention CN102269696A discloses a method for detecting dithiocarbamate pesticide residues, which comprises: for cruciferous crops such as Chinese cabbage, radish and the like, 50-100g of sample is taken, added with water and heated for micro-boiling for 15-25 minutes; distilling and extracting samples with darker colors such as purple perilla and the like; and meanwhile, preparing a working curve for colorimetric analysis. Although the problem of false positive in the colorimetric method is solved to a certain extent, the practical operation is still more complicated, the detection result speed is slow, the cost is higher, and the rapid detection of dithiocarbamate pesticides contained in fruits and vegetables is not facilitated.
Therefore, there is a need for a sensitive technique for rapidly detecting the residual dithiocarbamate pesticides present in fruits and vegetables.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel method for rapidly detecting dithiocarbamate pesticides, which has the advantages of simple operation and low cost on the premise of high detection accuracy, high detection sensitivity and low detection lower limit.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a detection method of dithiocarbamate pesticides in agricultural products comprises the following steps:
1) mixing an agricultural product to be detected with an organic solvent, a first salt bag and a second salt bag, so that a dithiocarbamate pesticide enters the organic solvent, and extracting, filtering or centrifuging to obtain a clear liquid detection sample, wherein the first salt bag is used for destroying the cell structure of the agricultural product, and the second salt bag is used for absorbing water in the agricultural product;
2) immersing an active area of the SERS substrate in the liquid detection sample obtained in the step (1) for a preset time, so that dithiocarbamate pesticide molecules are adsorbed or grabbed to the surface of the SERS substrate;
3) and (3) drying the SERS substrate obtained in the step (2) and then carrying out Raman detection.
According to some preferred aspects of the invention, the agricultural product is a vegetable, fruit, crop, in particular a banana, a dragon fruit, a mango, an apple, a pear, a cucumber, a tomato, a fresh corn, a soybean, or the like.
In the present invention, the "dithiocarbamate pesticides" include maneb, zineb, amobam, maneb, dysosram, mancozeb, metiram, propineb, thiram, sodium thiram, potassium thiram, ziram, arsine, ferrothiram, arsine, and the like.
According to some specific and preferred aspects of the invention, the first salt package comprises one of a nitrate, a carbonate, a silicate, an acetate, a phosphate, a halide salt, or any combination thereof.
According to some specific and preferred aspects of the invention, the second salt comprises one of sodium sulfate, calcium chloride, magnesium chloride, or any combination thereof.
According to some specific and preferred aspects of the present invention, the organic solvent is selected from one of ethyl acetate, acetonitrile, dimethylsulfoxide, dimethylformamide and dimethylacetamide, or any combination thereof.
According to some preferred aspects of the invention, in the step (1), the feeding mass ratio of the first salt package to the agricultural product to be tested is 0.004-40: 1, preferably the feeding mass ratio of the first salt package to the agricultural product to be tested is 0.01-30: 1, more preferably the feeding mass ratio of the first salt package to the agricultural product to be tested is 0.1-20: 1, and further preferably the feeding mass ratio of the first salt package to the agricultural product to be tested is 0.1-10: 1.
According to some preferred aspects of the invention, in the step (1), the feeding mass ratio of the second salt package to the agricultural product to be tested is 0.008-80: 1, preferably the feeding mass ratio of the second salt package to the agricultural product to be tested is 0.01-50: 1, more preferably the feeding mass ratio of the second salt package to the agricultural product to be tested is 0.1-30: 1, and further preferably the feeding mass ratio of the second salt package to the agricultural product to be tested is 0.2-10: 1.
According to some preferred aspects of the present invention, the detection method further comprises a step of purifying the liquid detection sample, wherein the purification comprises drying and/or adsorbing the liquid detection sample by using a filler, and then adding an alcohol polar solvent and/or an ether polar solvent to prepare a sample for raman detection.
According to some specific and preferred aspects of the present invention, the alcoholic polar solvent is methanol and/or ethanol.
According to some specific and preferred aspects of the present invention, the ether-based polar solvent includes ethylene glycol monomethyl ether and/or tert-butyl monomethyl ether.
According to some specific and preferred aspects of the present invention, the filler is one selected from the group consisting of C18 filler, PSA filler, graphitized carbon, alumina and PEP filler, or any combination thereof.
According to some specific and preferred aspects of the present invention, the detection method further comprises plotting a standard curve between the intensity of characteristic peaks and spiking concentrations for different types of dithiocarbamate pesticides in the agricultural product.
According to a specific aspect of the invention, the characteristic peak of the thiram and thiram surface enhanced Raman spectrum is 933cm-1，1138cm-1，1370cm-1，1497cm-1The method is characterized in that thiram with different concentrations is added in the fruits and vegetables, the characteristic peak intensity of the thiram is in direct proportion to the added standard concentration, and the standard curve can be drawn for quantitative analysis of the thiram in the fruits and vegetables.
According to a specific aspect of the invention, the characteristic peak of the metiram surface enhanced Raman spectrum is 491cm-1，1228cm-1，1280cm-1，1316m-1，1442cm-1，1529cm-1The metiram with different concentrations is added in the fruits and vegetables, the characteristic peak intensity of the metiram is in direct proportion to the added standard concentration, and the method can be used for quantitative analysis of the metiram in the fruits and vegetables after a standard curve is drawn.
According to a specific aspect of the invention, the characteristic peak of the propineb surface enhanced Raman spectrum is 471cm-1，1472cm-1The propineb with different concentrations is added in the fruit and vegetable, the characteristic peak intensity is in direct proportion to the added standard concentration, and the standard curve is drawn and may be used in the quantitative analysis of propineb in fruit and vegetable.
According to some preferred aspects of the invention, the SERS substrate is made by drying a noble metal sol.
According to some preferred aspects of the present invention, the SERS substrate comprises a substrate and a noble metal nanoparticle or noble metal layer disposed on the substrate.
According to some preferred aspects of the present invention, the SERS substrate comprises a substrate having a plurality of pits and clusters of noble metal nanoparticles self-assembled within the pits. The pits may be made by nanoimprint, plasma etching, ultraviolet etching, chemical etching, laser etching, mechanical drilling, mechanical stamping, or electrochemical methods.
According to some specific aspects of the present invention, the noble metal sol may be prepared by adding a solution containing a noble metal salt including silver nitrate, chloroauric acid, and the like to a citrate solution.
According to some specific aspects of the invention, the noble metal comprises gold, silver, or the like; the noble metal nanoparticle cluster is composed of a plurality of noble metal nanoparticles; noble metal nanoparticles, i.e., nanoparticles of noble metal materials; the noble metal layer is formed by coating or infiltrating the noble metal.
According to some particular aspects of the invention, the citrate salt may be sodium citrate or the like.
According to some embodiments of the invention, the method of self-assembly comprises dropping, spin coating, printing, injecting or spraying a dispersion containing nanoparticles onto the substrate surface, or alternatively, immersing the substrate surface in a dispersion of the nanoparticles and removing the solvent of the dispersion by evaporation.
There are various ways of the above immersion, for example, immersing the substrate in the dispersion, taking out the substrate, and volatilizing the solvent; or immersing the surface of the substrate into the dispersion liquid, taking out the substrate and volatilizing the solvent; alternatively, a layer of the dispersion is dropped on the surface of the substrate, and then the solvent is volatilized. The spin coating refers to spin coating of the dispersion on the surface of the substrate by a device.
According to some preferred aspects of the present invention, the plurality of dimples on the substrate are different in at least one of size, shape, and pitch between the dimples and arrangement of the plurality of dimples.
According to some preferred aspects of the present invention, the plurality of pits in the substrate are regularly varied in one or more of size, shape, interval between two adjacent pits, and arrangement of the plurality of pits.
According to some preferred aspects of the present invention, any two of the pits on the substrate have a size difference of 0-1000nm and have the same shape, and a spacing difference between any two adjacent pits is 0-500 nm; wherein the size of the pit comprises the diameter of the pit and the depth of the pit.
According to some preferred aspects of the present invention, the diameter of the pits is 50nm to 500nm, the distance between the pits is 5nm to 50nm, the number of the noble metal nanoparticles in the noble metal nanoparticle cluster is 3 to 15, and the particle diameter of each noble metal nanoparticle is 30nm to 120 nm.
According to some preferred aspects of the invention, the depth of the pits is 90 to 10000 nm.
According to some preferred aspects of the present invention, the upper surface area of the substrate is 4 to 400mm2(ii) a More preferably, the upper surface area of the substrate is 16-100mm2(ii) a Further preferably, the upper surface area of the substrate is 16-36mm2。
According to some specific aspects of the invention, the substrate is a silicon, glass, PDMS, PMMA, Al, alumina or other substrate.
In the invention, the distance between the pits refers to the minimum spacing distance between two adjacent pits, more specifically refers to the minimum distance in a plurality of distances between any point on the upper edge of one pit and any point on the upper edge of the adjacent pit; the diameter of the pit refers to the largest distance among a plurality of distances between any two points on the upper edge of the pit.
According to some preferred aspects of the invention, the SERS substrate is a hydrophobic SERS substrate. In the present invention, the hydrophobic modification method used in the hydrophobic SERS substrate may be a hydrophobic modification method commonly used in the art.
In the present invention, the SERS substrate (surface enhanced raman scattering substrate) can give structural information of molecules at a molecular level, and thus can discriminate the concentration of a compound from vibration information of molecules adsorbed on a metal surface.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides a method for extracting and detecting dithiocarbamate pesticides in agricultural products by using Surface Enhanced Raman Spectroscopy (SERS), aiming at the defects of the existing method for extracting and detecting dithiocarbamate pesticides in agricultural products, and simultaneously aiming at the detection requirement of surface enhanced Raman in the prior art, a corresponding rapid pretreatment step is designed, so that a rapid and effective SERS solution is formed, the problem of a difficulty in practical application is solved, the steps of rapidly extracting and detecting samples by using a first salt bag and a second salt bag are innovatively provided, the interference of complex matrixes in agricultural products, particularly fruits and vegetables is solved, the influence of conventional Raman of agricultural products is avoided, and the method has the advantages of simple steps, short analysis time, good selectivity, no need of large-scale instruments, satisfaction of national standard limit requirements, realization of rapid and accurate detection of dithiocarbamate pesticides in field food and the like, and can realize rapid and accurate detection of dithiocarbamate pesticides in field food, and has the advantages of high detection accuracy, The method has the advantages of simple operation and low cost on the premise of low detection lower limit, and particularly the detection lower limit can be as low as 0.01 mg/kg.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts;
fig. 1 is a surface enhanced raman spectrum of a standard thiram, metiram, propineb, in the detection method of the present invention; :: thiram; it: metiram; a tangle-solidup: propineb.
FIG. 2 is a surface enhanced Raman spectrum of 0.5mg/L thiram in red-core dragon fruit according to the detection method of the present invention;
FIG. 3 is a surface enhanced Raman spectrum of banana labeled with 1mg/L metiram in the detection method provided by the present invention;
FIG. 4 shows that the pears plus standard double-component pesticide of the invention contains thiram 0.25ppm, and metiram (A5 ppm), (B2.5 ppm) and (C0.5 ppm) in different concentrations. :: thiram; it: a surface enhanced raman spectrogram of metiram;
FIG. 5 shows that the concentration of different thiram in mango is 1370cm-1A peak intensity relationship graph;
FIG. 6 is an SEM image of a SERS substrate I prepared according to the invention;
FIG. 7 is an SEM image of a SERS substrate II prepared according to the invention;
FIG. 8 is an SEM image of a SERS substrate III prepared according to the invention;
FIG. 9 is a schematic structural diagram of a SERS substrate IV prepared by the invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following examples, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
Preparing nano silver sol:
1mL of silver nitrate aqueous solution with the mass concentration of 1% is added into a 100mL three-neck flask and diluted to 100 mL; the solution was heated to boiling and 1% strength sodium citrate solution was added under constant reflux and vigorous stirring. The solution gradually changed from colorless to pale blue. Timing after color change, keeping the boiling state of the system for 15 min under the stirring condition, and then naturally cooling to room temperature to obtain the silver sol.
Preparing nano gold sol:
adding 1mL of chloroauric acid aqueous solution with the mass concentration of 1% into a 100mL three-neck flask, and diluting to 100 mL; the solution was heated to boiling and 1% strength sodium citrate solution was added under constant reflux and vigorous stirring. The solution gradually changed from light yellow to wine red. Timing is started after color change, the boiling state of the system is kept for 15 min under the stirring condition, then the system is naturally cooled to the room temperature to obtain gold sol, and the particle size of Au can be adjusted by adjusting the amount of added sodium citrate.
Self-assembly of the nano sol:
cutting the glass slide into 2cm by 2cm square chips, washing with detergent, and washing with water2And (5) drying. Then using O2The plasma cleaner was used for 5 min. Soaking in 5% 3-aminopropyltriethoxysilane water solution for 1min, washing with ultrapure water for 2 times, and washing with N2And (5) drying. And placing the substrate in silver sol for 3h, taking out the silver sol, and washing with a large amount of water to obtain an SERS substrate I, as shown in FIG. 6.
Self-assembly of the nano sol:
nano-imprinting a chip with regular holes 0.4cm by 0.4cm square chip with a pore diameter of 100nm, a pore depth of 60nm and a spacing of 90 nm. Cleaning with detergent, N2And (5) drying. Then using O2The plasma cleaner was used for 5 min. And then soaking in gold sol for 3h, taking out and washing with a large amount of water to obtain an SERS substrate II, as shown in FIG. 7.
Nano-imprinting a chip with regular holes 0.4cm by 0.4cm square chip with a pore diameter of 500nm, a pore depth of 200nm and a spacing of 450 nm. Cleaning with detergent, N2And (5) drying. Then using O2The plasma cleaner was used for 5 min. And then soaking in gold sol for 3h, taking out and washing with a large amount of water to obtain an SERS substrate III, as shown in FIG. 8.
Example 1
The method for detecting the dithiocarbamate pesticides in the agricultural products comprises the following steps:
weighing 10g of red-heart pitaya, crushing (thiram, 0.5 mg/L), adding 10ml of acetonitrile solution, adding 2.5g of sodium chloride solid, shaking for 2min, adding 5g of anhydrous sodium sulfate, fully shaking the sample for 3min, and centrifuging at 5000rpm for 5 min;
2, taking the upper solution (namely acetonitrile solvent phase) in a test tube, and drying by nitrogen;
3, taking 200 mu L of methanol in the test tube, and oscillating for several times to be used as a solution to be detected;
and 4, soaking the SERS substrate I in 150 mu L of the solution to be tested for 10min, taking out, cleaning with ethanol, drying in the air, and testing with a Raman spectrometer. A surface enhanced raman spectrum as shown in figure 2 was obtained.
Example 2
The method for detecting the dithiocarbamate pesticides in the agricultural products comprises the following steps:
weighing 10g of banana, crushing (metiram, 1 mg/L), adding 10ml of acetonitrile solution, adding 2.0g of potassium chloride solid, shaking for 2min, adding 4g of anhydrous magnesium sulfate, fully shaking the sample for 3min again, and centrifuging at 5000rpm for 5 min;
2, filtering 2mL of the upper layer solution (namely acetonitrile solvent phase) to obtain a solution to be detected;
and 3, soaking the SERS substrate II in 200 mu L of the solution to be tested for 10min, taking out, cleaning with ethanol, drying in the air, and testing with a Raman spectrometer. A surface enhanced raman spectrum as shown in figure 3 was obtained.
Example 3
The method for detecting the dithiocarbamate pesticides in the agricultural products comprises the following steps:
weighing 10g of three parts of bananas, crushing (wherein A is 0.25mg/L of thiram and 5mg/L of metiram, B is 0.25mg/L of thiram and 2.5mg/L of metiram, C is 0.25mg/L of thiram and 0.5mg/L of metiram), adding 10ml of acetonitrile solution, adding 2.0g of potassium nitrate solid, shaking for 2min, adding 4g of anhydrous calcium chloride, fully shaking the sample for 3min again, and centrifuging for 5min at 5000 rpm;
2, filtering 2mL of the upper layer solution (namely acetonitrile solvent phase) to obtain a solution to be detected;
and 3, soaking the SERS substrate III in 200 mu L of the solution to be tested for 10min, taking out, cleaning with ethanol, drying in the air, and testing with a Raman spectrometer. The surface enhanced raman spectrum shown in fig. 4 was obtained, and the raman spectrum of both mixtures was clearly seen.
Example 4
The method for detecting the dithiocarbamate pesticides in the agricultural products comprises the following steps:
1, weighing 10g of mango (respectively added with 0mg/L, 0.5mg/L, 1mg/L, 5mg/L and 10 mg/L), adding 10ml of acetonitrile solution, adding 2.0g of potassium nitrate solid, shaking for about 2min, adding 4g of anhydrous calcium chloride, fully shaking the sample for about 3min again, and centrifuging at 5000rpm for 5 min.
Taking 3mL of the upper layer solution (namely acetonitrile solvent phase) and filtering to obtain a solution to be detected;
3, soaking the SERS substrate II in the 180 mu L of solution to be tested for 10min, taking out, cleaning with ethanol, drying in the air, and testing with a Raman spectrometer;
4, selecting 1370cm-1The intensity of the peak is linear as shown in FIG. 5, the fitting equation is y =28123-2=0.97811。
Example 5
Preparation of the SERS substrate: preparing pits by using a chemical etching method, 1: processing a required structure on a silicon or other substrate by means of electron beam etching and the like to be used as a template; 2: transferring a pattern, namely coating photoresist on the surface of a material to be processed, pressing a template on the surface of the material, and transferring the pattern onto the photoresist in a pressurizing mode; 3: processing a substrate, curing the photoresist by using ultraviolet light, removing a template, etching the photoresist which is not completely removed in the previous step by using etching liquid to expose the surface of a material to be processed, then processing by using a chemical etching method, removing all the photoresist after the completion, finally obtaining the substrate with a high-precision pit, cleaning the substrate by using a detergent, and removing N2Blow-drying, then using O2And (3) treating for 5min by using a plasma cleaning machine, soaking in the gold sol prepared by the preparation method of the nanogold sol for 2h, taking out, cleaning with a large amount of water to obtain an SERS substrate IV, wherein the obtained structure is shown in figure 9. The SERS substrate IV has higher SERS activity and can be used for SERS traceAnd (6) detecting.
The prepared SERS substrate IV overcomes the defect that the homogeneous SERS substrate in the prior art can only act on a single substance, and particularly, operations such as rapid detection, catalysis and the like can not be carried out under unknown substance types and micro-contents; the SERS substrate with the change is adopted, so that the SERS substrate has the advantages of wide matching range and strong universality, can simultaneously have the functions of catalyzing, detecting, degrading and the like on various substances, and greatly reduces the workload and the cost. The method is particularly suitable for detecting dithiocarbamate pesticides contained in agricultural products with unknown concentration and possibly low content, wherein the agricultural products can be vegetables, fruits and crops, and specifically can be bananas, dragon fruits, mangoes, apples, pears, cucumbers, tomatoes, fresh corns, soybeans and the like. The method specifically comprises the following steps: the method for detecting the dithiocarbamate pesticides in the agricultural products comprises the following steps:
weighing 10g of three parts of bananas, crushing (wherein A is 0.25mg/L of thiram and 5mg/L of metiram, B is 0.25mg/L of thiram and 2.5mg/L of metiram, C is 0.25mg/L of thiram and 0.5mg/L of metiram), adding 10ml of acetonitrile solution, adding 2.0g of potassium nitrate solid, shaking for 2min, adding 4g of anhydrous calcium chloride, fully shaking the sample for 3min again, and centrifuging for 5min at 5000 rpm;
2, filtering 2mL of the upper layer solution (namely acetonitrile solvent phase) to obtain a solution to be detected;
and 3, soaking the prepared SERS substrate IV in 200 mu L of the solution to be tested for 10min, taking out, cleaning with ethanol, drying in the air, and testing with a Raman spectrometer. The result shows that the Raman spectrum of the mixture of the two can be clearly seen, the detection speed is high, and the adaptability is strong.
The method utilizes the surface enhanced Raman spectrum, solves the interference of complex matrixes in agricultural products, particularly fruits and vegetables, has no influence of conventional Raman of the agricultural products, has the advantages of simple steps, short analysis time, good selectivity, no need of large instruments, satisfaction of national standard limit requirements, realization of rapid and accurate detection of dithiocarbamate pesticides in field food, and the like, and has the advantages of simple operation and low cost on the premise of high detection accuracy, high detection sensitivity and low detection lower limit.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (4)
1. A detection method of dithiocarbamate pesticides in agricultural products is characterized by comprising the following steps:
1) mixing an agricultural product to be detected with an organic solvent, a first salt bag and a second salt bag, so that a dithiocarbamate pesticide enters the organic solvent, and extracting, filtering or centrifuging to obtain a clear liquid detection sample, wherein the first salt bag is used for destroying the cell structure of the agricultural product, and the second salt bag is used for absorbing water in the agricultural product; the first salt package comprises one or any combination of nitrate, carbonate, silicate, acetate, phosphate and halide salt, the second salt package comprises one or any combination of sodium sulfate, calcium chloride and magnesium chloride, and the organic solvent is one or any combination of ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethyl formamide and dimethyl acetamide;
2) immersing an active area of the SERS substrate in the liquid detection sample obtained in the step 1) for a preset time to enable dithiocarbamate pesticide molecules to be adsorbed or grabbed onto the surface of the SERS substrate; the SERS substrate comprises a substrate with a plurality of pits and a noble metal nanoparticle cluster self-assembled in the pits, wherein the plurality of pits on the substrate are regularly changed in one or more of the size, the shape, the interval between two adjacent pits and the arrangement mode of the plurality of pits, and the size of each pit comprises the diameter of each pit and the depth of each pit;
3) drying the SERS substrate obtained in the step 2), and then carrying out Raman detection.
2. The method for detecting dithiocarbamate pesticides in agricultural products according to claim 1, wherein the method further comprises a step of purifying the liquid detection sample, wherein the purification comprises drying and/or adsorbing the liquid detection sample with a filler, and adding an alcohol polar solvent and/or an ether polar solvent to prepare a sample for raman detection.
3. The method for detecting dithiocarbamate pesticides in agricultural products according to claim 2, wherein the alcohol polar solvent is methanol and/or ethanol; and/or the ether polar solvent comprises ethylene glycol monomethyl ether and/or tert-butyl monomethyl ether; and/or the filler is one or any combination of C18 filler, PSA filler, graphitized carbon, alumina and PEP filler.
4. The method for detecting dithiocarbamate pesticides in agricultural products according to claim 1, wherein the diameter of the pits is 50nm to 500nm, the distance between the pits is 5nm to 50nm, the number of noble metal nanoparticles in the noble metal nanoparticle cluster is 3 to 15, and the particle diameter of each noble metal nanoparticle is 30nm to 120 nm.
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