Instant detection sensor and application thereof in chlorfenapyr poisoning detection
By loading AuRD on ZIF-67 and modifying the MCE membrane instant detection sensor, using SERS technology, the existing nitrile detection methods are solved, and the equipment is complex, and the rapid and sensitive detection of nitrile is achieved, with excellent thermal stability and precision.
Patent Information
- Application Number
- CN202411970832.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-30
- Publication Date
- 2025-05-13
- Estimated Expiration
- 2044-12-30
AI Technical Summary
The existing method of mites detection is time-consuming, requires expensive instruments and complex sample preparation processes, making it difficult to quickly and sensitively detect mites in human serum and urine in clinical environments.
The instant detection sensor with AuRD load on ZIF-67 is adopted, and the surface-enhanced Raman spectroscopy (SERS) technology is combined with MCE film modification to achieve rapid detection of nitrile.
It realizes rapid and sensitive detection of nitrile, with excellent thermal stability, spatial uniformity and precision, and is suitable for qualitative and quantitative analysis in biological fluids.
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Figure CN119985431A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of toxicity detection, in particular to an instant detection sensor and application thereof in the detection of acarid poisoning. Background Art
[0002] Chlorfenapyr is a globally used N-substituted halogenated pyrrole insecticide, with the international joint name of 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile). Chlorfenapyr is an insecticide that can effectively kill insects by causing rhabdomyolysis, metabolic acidosis and renal failure after oral or contact exposure. Chlorfenapyr has been widely used in areas with high resistance to pyrethroids, and China is the largest market for chlorfenapyr.
[0003] In recent years, the incidence of chlorfenapyr poisoning in humans due to suicide or accidental ingestion has been increasing. The symptoms of chlorfenapyr poisoning patients are mild and atypical in the early stages, especially in patients exposed to low doses, and their symptoms may be ignored by doctors, resulting in delayed treatment; once chlorfenapyr toxicity involves the hypothalamic temperature regulation center and the medullary respiratory and cardiac centers, patients often experience high fever coma or even death; chlorfenapyr poisoning survivors usually experience persistent neurological sequelae. In order to diagnose and rescue chlorfenapyr poisoning patients in a timely manner, rapid detection of chlorfenapyr poisoning is an important prerequisite.
[0004] At present, the main detection methods of chlorfenapyr are liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), but these methods are very time-consuming and require expensive instruments and complex sample preparation processes; in addition, the existing chlorfenapyr detection methods are mainly for food and environmental samples, and the detection methods are time-consuming and also require expensive instruments and complex sample preparation processes. Therefore, it is urgent to develop qualitative and quantitative detection technologies for chlorfenapyr in biological fluids that can be applied clinically. Summary of the invention
[0005] In view of the deficiencies of the prior art, the present invention provides an instant detection sensor capable of rapidly and sensitively detecting chlorfenapyr in human serum and urine.
[0006] The technical solution of the present invention is as follows:
[0007] An instant detection sensor was developed by loading AuRD on ZIF-67 and then co-modifying the MCE membrane.
[0008] Preferably, the mass ratio between AuRD and ZIF-67 is 100:(1-1.5).
[0009] Preferably, the instant detection sensor is applied based on surface enhanced Raman spectroscopy.
[0010] The preparation method of the instant detection sensor comprises the following steps:
[0011] (1) Preparing AuRD solution;
[0012] (2) preparing a ZIF-67 solution;
[0013] (3) After mixing the AuRD solution and the ZIF-67 solution, drop them evenly on the MCE membrane and let them stand.
[0014] Preferably, the method for preparing the AuRD solution in step (1) comprises the following steps:
[0015] i. Preparation of HAuCl 4 and CTAC mixed solution; prepare NaBH 4 solution, precooled; under stirring, NaBH was added to the mixed solution 4 solution to obtain a brown seed solution, which was aged at 30-35°C for 1-1.2 hours to obtain a gold seed solution;
[0016] ii. Prepare two containers, add CTAC and water to each container, and place them in a water bath at 30-35°C; while in the water bath, continue to add HAuCl 4 solution, NaBr solution, and ascorbic acid solution;
[0017] iii. Mark the two containers of step ii as A and B respectively; add the gold seed solution of step i to container A under oscillation to obtain a light pink solution; transfer the light pink solution to container B, mix thoroughly, let stand for 15 to 20 minutes, and centrifuge at 6000 to 8000 rpm for 5 to 10 minutes to obtain AuRD precipitate; dissolve the precipitate in water to obtain AuRD solution.
[0018] Further preferably, the HAuCl in step i 4 , CTAC, NaBH 4 The molar ratio between them is 2.5:1000:9.
[0019] Further preferably, in step ii, CTAC, HAuCl 4 The molar ratio of NaBr and ascorbic acid is 1000:2.5:0.1:1.5.
[0020] Preferably, the method for preparing the ZIF-67 solution in step (2) comprises the following steps:
[0021] S1. preparing cobalt nitrate hexahydrate solution and 2-methylimidazole solution respectively;
[0022] S2. The cobalt nitrate hexahydrate solution and the 2-methylimidazole solution of step S1 are mixed and stirred at room temperature at 1000 to 1500 rpm for 6 to 6.5 h;
[0023] S3. Centrifuge at 6000-8000 rpm for 10-15 min to obtain ZIF-67 precipitate; wash and dissolve the precipitate with ethanol to obtain ZIF-67 solution.
[0024] Further preferably, in step S2, the mass ratio between the cobalt nitrate hexahydrate and 2-methylimidazole is 0.45:5.5.
[0025] Preferably, step (3) comprises the following steps: mixing the AuRD solution of step (1) and the ZIF-67 solution of step (2), centrifuging at 6000-8000 rpm for 10-15 min, standing to separate the layers, and obtaining an upper clear liquid and a lower mixed liquid; uniformly dropping the lower mixed liquid on the MCE membrane, and standing for 20-30 min to obtain an instant detection sensor.
[0026] Application of the instant detection sensor in the detection of chlorfenapyr poisoning.
[0027] Preferably, the application method comprises the following steps: placing the instant detection sensor on a surface enhanced Raman spectrometer, dropping a chlorfenapyr sample on the surface of the instant detection sensor, and detecting chlorfenapyr poisoning by the signal intensity of the Raman spectrum.
[0028] Beneficial effects:
[0029] The invention discloses an instant detection sensor based on surface enhanced Raman spectroscopy (SERS), which can rapidly and sensitively detect chlorfenapyr in human serum and urine, and the instant detection sensor has excellent thermal stability, spatial uniformity and precision. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 The structural characterization diagram of AuRD@ZIF-67 / MCE;
[0031] Figure 2 is the SERS signal intensity of the sensor prepared using different gold nanostructures;
[0032] Figure 3 is the SERS signal intensity at different deposition times when 50 μL ZIF-67 solution is added;
[0033] Figure 4 Optimize the detection pH of AuRD@ZIF-67 / MCE;
[0034] Figure 5Optimize the detection temperature of AuRD@ZIF-67 / MCE;
[0035] Figure 6 is the adsorption time of AuRD@ZIF-67 / MCE on chlorfenapyr sample;
[0036] Figure 7 is the relationship between the concentration of chlorfenapyr sample and the SERS signal intensity on AuRD@ZIF-67 / MCE;
[0037] Figure 8 To test the thermal stability of AuRD@ZIF-67 / MCE;
[0038] Fig. 9 To detect the spatial uniformity of AuRD@ZIF-67 / MCE;
[0039] Fig.10 This is the precision detection of AuRD@ZIF-67 / MCE. DETAILED DESCRIPTION
[0040] The following is explained in conjunction with specific embodiments:
[0041] (1) Explanation of relevant terms:
[0042] AuRD (Au Rhombic Dodecahedra): gold nano-rhombic dodecahedra;
[0043] ZIF-67 (Zeolitic Imidazole Framework-67): a metal organic framework (MOF);
[0044] MCE (Mixed Cellulose Ester) membrane: a mixed cellulose ester membrane.
[0045] (2) Source of experimental materials:
[0046] MCE membrane: purchased from Haining Delv New Material Technology Co., Ltd.;
[0047] Surface enhanced Raman spectrometer: QE Pro, Ocean Optics;
[0048] Chlorfenapyr standard sample: purchased from Beijing North Weiye Metrology Technology Research Institute; Chlorfenapyr standard sample was dissolved in the urine of healthy volunteers to prepare chlorfenapyr standard samples of different concentrations.
[0049] Example 1: Preparation of instant detection sensor AuRD@ZIF-67 / MCE
[0050] The preparation method is specifically carried out according to the following steps:
[0051] 1. Preparation of AuRD solution:
[0052] Refer to the literature "A Comparative Study of Gold Nanocubes, Octahedra, and RhombicDodecahedra as Highly Sensitive SERS Substrates".
[0053] i. Prepare 10 mL containing 0.25 mM HAuCl 4 and 0.10M CTAC; prepare 10mL of 0.02M NaBH 4 The solution was precooled at 4°C. Under stirring, 0.45 mL of NaBH 4 Solution to obtain a brown seed solution, which was aged at 30°C for 1 hour to obtain a gold seed solution;
[0054] ii. Prepare two containers, add 0.32g CTAC and 9.545mL water to each container, and place in a water bath at 30°C; in the water bath, continue to add 250μL of 0.01M HAuCl 4 solution, 10 μL of 0.01 M NaBr solution, and 150 μL of 10 mM ascorbic acid solution;
[0055] iii. The two containers in step ii were marked as A and B respectively; under oscillation, 45 μL of the gold seed solution in step i was added to container A to obtain a light pink solution; 45 μL of the light pink solution was transferred to container B, and after thorough mixing, the mixture was allowed to stand for 15 min and centrifuged at 6000 rpm for 5 min to obtain 20.15 g of AuRD precipitate; the precipitate was dissolved in 1 mL of water to obtain an AuRD solution.
[0056] 2. Preparation of ZIF-67 solution:
[0057] Refer to the literature "Point-of-Use SERS Approach for Efficient Determination andRemoval of Phthalic Acid Esters Based on a Metal-Organic Framework-CoatedMelamine Sponge".
[0058] S1. Dissolve 0.45 g of cobalt nitrate hexahydrate in 3 mL of water to obtain a cobalt nitrate hexahydrate solution, and dissolve 5.5 g of 2-methylimidazole in 20 mL of water to obtain a 2-methylimidazole solution;
[0059] S2. The cobalt nitrate hexahydrate solution and the 2-methylimidazole solution of step S1 were mixed and stirred at room temperature at 1000 rpm for 6 h;
[0060] S3. Centrifuge at 6000rpm for 10min to obtain 23.89g of ZIF-67 precipitate; wash the precipitate with ethanol three times, and finally dissolve it with 5mL of ethanol to obtain ZIF-67 solution; take 50μL of ZIF-67 solution for later use.
[0061] 3. Preparation of instant detection sensor AuRD@ZIF-67 / MCE:
[0062] The AuRD solution prepared above and 50 μL ZIF-67 solution were evenly mixed, centrifuged at 8000 rpm for 10 min, and allowed to stand for stratification to obtain an upper clear liquid and a lower mixed liquid; the lower mixed liquid was evenly dripped onto the MCE membrane and allowed to stand for 30 min to obtain the instant detection sensor AuRD@ZIF-67 / MCE.
[0063] The structure of the instant detection sensor AuRD@ZIF-67 / MCE prepared above was characterized by Hitachi Regulus 8100 instrument. Figure 1 As shown. Figure 1 It can be seen that the MCE membrane presents a porous structure and can accommodate a considerable amount of AuRD@ZIF-67 composites, and the AuRD@ZIF-67 composites are evenly distributed on the surface of the MCE membrane.
[0064] Example 2: Comparison of different gold nanostructures
[0065] According to the same preparation method as AuRD@ZIF-67 / MCE, the other two gold nanostructures, Au Nanocubes and AuNPs, were co-modified with ZIF-67 on the surface of MCE membrane to obtain sensors Au Nanocubes@ZIF-67 / MCE and AuNPs@ZIF-67 / MCE, respectively.
[0066] Among them, Au Nanocubes were prepared according to the literature "A Comparative Study of Gold Nanocubes, Octahedra, and Rhombic Dodecahedra as Highly Sensitive SERS Substrates"; AuNPs were prepared according to the literature "Rapid identification and quantification of diquat inbiological fluids within 30s using a portable Raman spectrometer".
[0067] The sensors Au Nanocubes@ZIF-67 / MCE, AuNPs@ZIF-67 / MCE and AuRD@ZIF-67 / MCE prepared in Example 1 were placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 785 nm laser, 135 mW intensity, and 20 seconds integration time. A 1 ppm chlorfenapyr standard sample was dripped onto the surface of each sensor, and the SERS signal intensity of each sensor was compared according to the same parameters (1090 cm -1 place).
[0068] The results are as follows Figure 2 As shown. Figure 2 It can be seen that compared with Au Nanocubes modification and AuNPs modification, AuRD@ZIF-67 / MCE has a higher -1 The strongest SERS signal is shown at .
[0069] Example 3: Optimization of ZIF-67 addition amount and detection conditions in AuRD@ZIF-67 / MCE
[0070] 10 μL, 50 μL, 100 μL and 500 μL of the ZIF-67 solution prepared in Example 1 were taken to prepare the instant detection sensor AuRD@ZIF-67 / MCE, and the preparation conditions and detection conditions of AuRD@ZIF-67 / MCE were optimized by different deposition times of 5 to 90 min.
[0071] The prepared AuRD@ZIF-67 / MCE was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 785 nm laser, 135 mW intensity, and 20 seconds integration time. A 1 ppm chlorfenapyr standard sample was dripped onto the surface of each sensor, and the SERS signal intensity of each sensor was compared (1090 cm -1 place).
[0072] The results are as follows Figure 3 As shown. Figure 3 It can be seen that when 50 μL ZIF-67 solution is added and the deposition time is 30 min, a satisfactory SERS signal intensity can be detected.
[0073] Example 4: Optimization of pH for detection of AuRD@ZIF-67 / MCE
[0074] The instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1 was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 785 nm laser, 135 mW intensity, and 20 seconds integration time. A 1 ppm chlorfenapyr standard sample with a pH value of 3 to 9 (the pH value was adjusted by adding different amounts of hydrochloric acid and sodium hydroxide solution) was dripped onto the surface of AuRD@ZIF-67 / MCE, and the SERS signals (1090 cm -1 place).
[0075] The results are as follows Figure 4 As shown. Figure 4 It can be seen that the detected SERS signal is the strongest when the pH value of the chlorfenapyr sample is 6. However, considering the detection efficiency, the pH value was not adjusted in the subsequent experiments.
[0076] Example 5: Optimization of detection temperature of AuRD@ZIF-67 / MCE
[0077] The instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1 was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 785 nm laser, 135 mW intensity, and 20 seconds integration time. The AuRD@ZIF-67 / MCE was heated to different temperatures between 10 and 35 °C in a water bath, and then a 1 ppm chlorfenapyr standard sample was dripped onto the surface of the AuRD@ZIF-67 / MCE at different temperatures to compare the SERS signals (1090 cm -1 place).
[0078] The results are as follows Figure 5 As shown. Figure 5 It can be seen that the SERS signal increases with the increase of the temperature of AuRD@ZIF-67 / MCE. When the temperature of AuRD@ZIF-67 / MCE is 25℃, a satisfactory SERS signal intensity can be detected.
[0079] Example 6: Adsorption of chlorfenapyr sample by AuRD@ZIF-67 / MCE
[0080] The instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1 was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 785 nm laser and 135 mW intensity. A 1 ppm chlorfenapyr standard sample was dripped on the surface of AuRD@ZIF-67 / MCE, and the integration time was adjusted to 20 s, 40 s, 60 s, 80 s, and 100 s, respectively. The SERS signal intensities (1090 cm -1 place).
[0081] The results are as follows Figure 6 As shown. Figure 6 It can be seen that AuRD@ZIF-67 / MCE achieved ultrafast adsorption of chlorfenapyr sample within 60 s and reached adsorption saturation within 100 s.
[0082] Example 7: Correlation coefficient and minimum detection limit of AuRD@ZIF-67 / MCE
[0083] The instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1 was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 785 nm laser, 135 mW intensity, and 20 seconds integration time; the purchased chlorfenapyr standard sample was dissolved in water, human serum, and human urine, respectively, to obtain chlorfenapyr standard sample aqueous solution, serum solution, and urine solution of different concentrations; the chlorfenapyr standard sample aqueous solution, serum solution, and urine solution of different concentrations were dripped on the surface of AuRD@ZIF-67 / MCE, and the SERS signal intensities (1090 cm -1 place).
[0084] The results are as follows Figure 7 As shown in Figures A and D, the standard samples of chlorfenapyr with different concentrations were analyzed at 1090 cm -1 Figures B and E show the SERS signal intensity of the chlorfenapyr standard sample serum solution at 1090 cm -1 Figures C and F show the SERS signal intensity of chlorfenapyr standard sample urine solutions at 1090 cm -1 The SERS signal intensity at .
[0085] Depend on Figure 7 Available, sample at 1090cm -1 The SERS signal intensity at the location is positively correlated with the logarithmic concentration of chlorfenapyr in the sample; Figure 7 The data in was used to calculate the recovery rate of chlorfenapyr in the sample (the recovery rate reflects the degree of recovery of the analyte in the sample detection process. The higher the recovery rate, the higher the analysis accuracy). The results are shown in Table 1 below:
[0086] Table 1. Recovery of chlorfenapyr in samples
[0087]
[0088] Depend on Figure 7 According to the data in Table 1 and the method detection limit (MDL) plan of the U.S. Environmental Protection Agency (EPA, 2016), the minimum detection limits of chlorfenapyr in aqueous solution of chlorfenapyr standard sample and biological samples (chlorfenapyr standard sample serum solution and urine solution) were determined to be 1.32 ppb and 1.81 ppb, respectively, by the EPA method (“Definition and Procedure for the Determination of the Method Detection Limit, Revision 2”), which met the requirements for real-time monitoring.
[0089] Example 8: Thermal stability test of AuRD@ZIF-67 / MCE
[0090] The instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1 was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 135 mW intensity and 20 seconds integration time. A 1 ppm chlorfenapyr standard sample was dripped on the surface of AuRD@ZIF-67 / MCE, and a 785 nm laser intensity was used to continuously irradiate the same point on the surface of AuRD@ZIF-67 / MCE for 30 times. The sample was detected at 1090 cm -1 The thermal stability of AuRD@ZIF-67 / MCE was evaluated by the SERS signal intensity at 400 nm.
[0091] The results are as follows Figure 8 As shown, A, B, and C are the waterfall diagram, heat map, and bar graph after 785nm laser was continuously irradiated at the same point on the surface of AuRD@ZIF-67 / MCE for 30 times. Figure 8 It can be obtained that the RSD (relative standard deviation) is 8.28%, which indicates that the instant detection sensor AuRD@ZIF-67 / MCE prepared in the present invention has excellent thermal stability.
[0092] Example 9: Spatial uniformity detection of AuRD@ZIF-67 / MCE
[0093] The instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1 was placed on a surface enhanced Raman spectrometer, and the parameters were adjusted to 135 mW intensity and 20 seconds integration time. A 1 ppm chlorfenapyr standard sample was dripped on the surface of AuRD@ZIF-67 / MCE, and 785 nm laser intensity was used to irradiate 30 random points on the surface of AuRD@ZIF-67 / MCE. The sample was detected at 1090 cm -1The SERS signal intensity at 400 nm was used to evaluate the point-to-point spatial uniformity of AuRD@ZIF-67 / MCE.
[0094] The results are as follows Fig. 9 As shown, A, B, and C are waterfall diagrams, heat maps, and bar graphs after 785nm laser irradiation at 30 random points on the surface of AuRD@ZIF-67 / MCE. Fig. 9 It can be obtained that the RSD (relative standard deviation) is 6.99%, which indicates that the instant detection sensor AuRD@ZIF-67 / MCE prepared in the present invention has excellent spatial uniformity.
[0095] Example 10: Precision detection of AuRD@ZIF-67 / MCE
[0096] The chlorpyrifos standard sample of unknown concentration was pretreated according to the record in the document "Bioaccumulation of Chloropyrifos Organo-pesticide and Its Toxicogenic Association with Antioxidant GSTP1 in Pakistani Pest Control Workers", and then the concentration was detected by surface enhanced Raman spectrometer and liquid chromatography-ultraviolet fluorescence (HPLC-UV), and the detected concentration results were compared; wherein the sensor used in the surface enhanced Raman spectrometer was the instant detection sensor AuRD@ZIF-67 / MCE prepared in Example 1.
[0097] The results are as follows Fig.10 As shown, Figure A is a comparison of the linear correlation of quantitative data by surface enhanced Raman spectroscopy and HPLC-UV spectroscopy, and Figure B is a comparison of the detection results of chlorfenapyr at different concentrations by surface enhanced Raman spectroscopy and HPLC-UV. Fig.10 It can be obtained that the detection results of the chlorfenapyr concentration by surface enhanced Raman spectroscopy and HPLC-UV are basically consistent, which shows that the instant detection sensor AuRD@ZIF-67 / MCE prepared in the present invention has good precision.
[0098] In summary, the instant detection sensor AuRD@ZIF-67 / MCE provided by the present invention can perform rapid and sensitive instant detection of chlorfenapyr, and the instant detection sensor has excellent thermal stability, spatial uniformity and precision. These properties provide strong evidence for the rapid qualitative and quantitative analysis of chlorfenapyr in biological fluids.
Claims
1. An instant detection sensor, characterized in that: AuRD was loaded on ZIF-67 and then co-modified with MCE membrane.
2. The instant detection sensor according to claim 1, characterized in that: The mass ratio between the AuRD and ZIF-67 is 100:(1-1.5).
3. The instant detection sensor according to claim 1, characterized in that: The instant detection sensor is based on surface enhanced Raman spectroscopy.
4. The method for preparing the instant detection sensor according to claim 1, characterized in that: The steps include: (1) Preparing AuRD solution; (2) preparing a ZIF-67 solution; (3) After mixing the AuRD solution and the ZIF-67 solution, drop them evenly on the MCE membrane and let them stand.
5. The preparation method according to claim 4, characterized in that: The method for preparing the AuRD solution in step (1) comprises the following steps: i. Prepare a mixed solution containing HAuCl4 and CTAC; prepare a NaBH4 solution and precool it; Under stirring conditions, adding NaBH4 solution to the mixed solution to obtain a brown seed solution, and aging the seed solution at 30-35° C. for 1-1.2 hours to obtain a gold seed solution; ii. Prepare two containers, add CTAC and water to each container, and place in a water bath at 30-35°C; in a water bath, continue to add HAuCl4 solution, NaBr solution and ascorbic acid solution to each container; iii. The two containers of step ii are marked as A and B; under shaking conditions, the gold seed solution of step i is added to container A to obtain a light pink solution; The light pink solution was transferred to container B, and after being fully mixed, it was allowed to stand for 15 to 20 minutes, and centrifuged at 6000 to 8000 rpm for 5 to 10 minutes to obtain AuRD precipitate; the precipitate was dissolved in water to obtain AuRD solution.
6. The preparation method according to claim 4, characterized in that: The preparation method of the ZIF-67 solution in step (2) comprises the following steps: S1. preparing cobalt nitrate hexahydrate solution and 2-methylimidazole solution respectively; S2. The cobalt nitrate hexahydrate solution and the 2-methylimidazole solution of step S1 are mixed and stirred at room temperature at 1000 to 1500 rpm for 6 to 6.5 h; S3. Centrifuge at 6000-8000 rpm for 10-15 min to obtain ZIF-67 precipitate; wash and dissolve the precipitate with ethanol to obtain ZIF-67 solution.
7. The preparation method according to claim 4, characterized in that: Step (3) comprises the following steps: mixing the AuRD solution of step (1) and the ZIF-67 solution of step (2), centrifuging at 6000-8000 rpm for 10-15 min, standing to separate the layers, and obtaining an upper clear liquid and a lower mixed liquid; dripping the lower mixed liquid evenly on the MCE membrane, and standing for 20-30 min to obtain an instant detection sensor.
8. Use of the instant detection sensor according to claim 1 in the detection of chlorfenapyr poisoning.
9. The use according to claim 8, characterized in that The application method comprises the following steps: placing the instant detection sensor on a surface enhanced Raman spectrometer, dropping a chlorfenapyr sample on the surface of the instant detection sensor, and detecting chlorfenapyr poisoning through the signal intensity of the Raman spectrum.
Citation Information
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