CN115678540A - Preparation method and application of ZIF-8 coating-based composite material - Google Patents
Preparation method and application of ZIF-8 coating-based composite material Download PDFInfo
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003792 electrolyte Substances 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 4
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- 239000000523 sample Substances 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 230000003321 amplification Effects 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a preparation method and application of a ZIF-8 coating-based composite material, wherein a solvent orientation method is adopted to prepare an MP QDs @ ZIF-8 composite material, and the method is simple; the in-situ generation of MPQDs by coating in the ZIF-8 hole is realized; adopt thePreparation of AFB from the composite 1 The MIP/MP QDs @ ZIF-8/GCE electrochemical luminescence sensor has excellent stability in a water environment, and the application range of the electrochemical luminescence sensor is improved; the AFB prepared from the ZIF-8 coated composite material 1 Application of-MIP/MP QDs @ ZIF-8/GCE electrochemical luminescence sensor in detection of aflatoxin B 1 High sensitivity and high anti-interference ability.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a ZIF-8 coating-based composite material, and application of the composite material in electrochemiluminescence sensing chemical analysis and aflatoxin B 1 (AFB 1 ) Application to monitoring.
Background
Halide perovskite materials represented by perovskite quantum dots have the advantages of good monochromaticity, adjustable light-emitting wavelength, high fluorescence Quantum Yield (QY) and the like, and are very promising luminescent probes for developing novel efficient electrochemical luminescence (ECL) sensors. Among various perovskite quantum dots, methylamine perovskite quantum dots (MP QDs) have narrower spectral width and defect-resistant photophysical characteristics, so that the methylamine perovskite quantum dots are widely concerned and have wide application prospects. The ECL sensor constructed by using the MP QDs as the ECL luminophor has the advantages of high sensitivity, good selectivity and the like.
However, all perovskite materials have different decomposition phenomena, especially when exposed to high humidity, high temperature, strong light, oxygen enrichment and the like, the decomposition process of the perovskite is accelerated, and the perovskite decay is particularly serious under the high humidity condition. On the premise that most of ECL analysis detection objects are biomolecules depending on water environments, MP QDs are easily decomposed due to structural instability and hygroscopicity, so that perovskites only generate transient ECL signals, and direct application of the perovskite in the water environments is limited.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a preparation method of a ZIF-8 coating-based composite material, and the prepared composite material can be stably applied to aqueous phase electrochemiluminescence detection and can be used for efficiently detecting low-concentration aflatoxin B 1 。
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of a ZIF-8 coating-based composite material comprises the following steps:
(1) Taking a proper amount of 2-methylimidazole and zinc nitrate hexahydrate, and respectively dissolving in methanol;
(2) Taking a proper amount of lead bromide and methylamine bromide, adding N, N-dimethylformamide and oleylamine, and stirring;
(3) Sequentially adding the methanol solution of 2-methylimidazole in the step (1) and the methanol solution of zinc nitrate hexahydrate in the step (2), and violently stirring at room temperature to obtain a precursor solution of MP QDs;
(4) Standing the precursor solution, removing the solvent, adding a proper amount of toluene, dissolving and stirring until the reaction is finished;
(5) And centrifuging the solution after the reaction to obtain a precipitate, washing the precipitate by adopting N, N-dimethylformamide and ethanol, and drying to obtain the ZIF-8 coated MP QDs composite material, namely the MP QDs @ ZIF-8 composite material.
Further, in the step (1), 2-methylimidazole and zinc nitrate hexahydrate are respectively dispersed in the methanol solution by using ultrasound.
The invention also provides application of the ZIF-8 coating-based MP QDs composite material in detecting aflatoxin B 1 A method of concentration comprising the steps of:
(1) The ZIF-8 coated MP QDs composite material is adopted to prepare the aflatoxin B 1 A molecularly imprinted electrochemiluminescence sensor (MIP/MP QDs @ ZIF-8/GCE);
(2) Constructing a three-electrode system by taking a Glassy Carbon Electrode (GCE) modified by the ZIF-8 coated MP QDs composite material as a working electrode, a platinum wire as an auxiliary electrode and Ag/AgCl as a reference electrode, placing the three electrodes in an electrolytic cell containing electrolyte, and connecting the three electrodes with an electrochemical luminoscope;
(3) Detecting, eluting and adsorbing a series of aflatoxins B with different concentrations in an electrochemical luminometer 1 The electrochemical luminescence signals of the MIP/MP QDs @ ZIF-8/GCE sensor are respectively marked as I ECL0 、I ECLn (n＝1、2、3…n)；
(4) Establishment of I ECL1 、I ECLn Difference of (a) with aflatoxin B 1 A quantitative relationship of concentration;
(5) Detecting the electrochemical luminescence signal of MIP/MP QDs @ ZIF-8/GCE sensor for adsorbing the sample solution by an electrochemical luminometer, and obtaining the aflatoxin B in the sample according to the quantitative relation 1 The concentration of (c).
Further, in the step (1), aflatoxin B is prepared 1 A method of molecularly imprinting an electrochemiluminescence sensor, comprising the steps of:
(11) Pretreating a Glassy Carbon Electrode (GCE);
(12) Modifying the prepared ZIF-8 coated MP QDs composite material solution on the surface of the pretreated glassy carbon electrode, and drying to form an MP QDs @ ZIF-8/GCE electrochemical luminescence sensor;
(13) Will contain the active component at a concentration of 10 -5 mol/L template molecule aflatoxin B 1 The molecular imprinting mixed solution is modified on the MP QDs @ ZIF-8/GCE, and then a layer of uniform and compact polymer film is formed by photopolymerization, so that the aflatoxin B based on the ZIF-8-coated MP QDs composite material is obtained 1 A molecular imprinting electrochemical luminescence sensor (MIP/MP QDs @ ZIF-8/GCE).
Further, in the step (2), the electrolyte is a PBS solution containing 0.01moL/L of co-reactant TPA and 0.1moL/L, and the pH value is 7.4; the photomultiplier of the electrochemical luminometer is 800V, the amplification level is 4, the potential scanning range is 0-1.5V, and the scanning speed is 200mV/s.
Further, in the step (12), the ZIF-8 coated MP QDs composite is dissolved in water to obtain a composite solution.
Further, in the step (13), the molecular imprinting mixed solution containing the template molecule is prepared from a template molecule of aflatoxin B 1 And a molecularly imprinted polymeric solution.
The preparation method of the ZIF-8-coated composite material has the beneficial effects that the MP QDs @ ZIF-8 composite material is prepared by adopting a solvent orientation method, so that the in-situ generated MP QDs are coated in the ZIF-8 holes, the ZIF-8 has excellent coating capability, and the dissolution of the MP QDs in a water environment is preventedTherefore, the water phase stability of the MP QDs @ ZIF-8 composite material prepared by the embodiment of the invention is greatly improved; the preparation process is simple; the MIP/MP QDs @ ZIF-8/GCE electrochemical luminescence sensor prepared from the ZIF-8 coated MP QDs composite material has good water phase stability, and the application range is improved; for detecting aflatoxin B 1 Its advantages are low limit of detection, high sensitivity and high anti-interference power.
Drawings
FIG. 1 shows a preparation method of a ZIF-8-coated composite material, an electrochemiluminescence sensor construction method and an application of the composite material in detection of aflatoxin B in corn 1 A flow chart of (1);
FIG. 2 is a Transmission Electron Microscope (TEM) image of an MP QDs @ ZIF-8 composite material prepared by an example of the present invention;
FIG. 3 is a partial enlarged view of the MP QDs @ ZIF-8 composite material Transmission Electron Microscope (TEM) of FIG. 2 according to the embodiment of the present invention;
FIG. 4 shows an electrochemical luminescence signal of an MIP/MP QDs @ ZIF-8/GCE sensor prepared from the MP QDs @ ZIF-8 composite material according to the embodiment of the invention along with AFB 1 A line graph of change in concentration;
FIG. 5 is an electrochemical luminescence signal change diagram of a MIP/MP QDs @ ZIF-8/GCE sensor constructed by the MP QDs @ ZIF-8 composite material along with a modified GCE process according to an embodiment of the invention;
FIG. 6 is a Transmission Electron Microscope (TEM) image of single MP QDs prepared in a comparative example of the present invention;
FIG. 7 is a comparison graph of signal response stability of an electrochemiluminescence sensor constructed by MP QDs @ ZIF-8 composite material prepared by the method of the embodiment of the invention and single MP QDs prepared by the comparative example.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example one
Referring to the attached figure 1, the embodiment of the invention provides a preparation method of a ZIF-8 coating-based composite material, which comprises the following steps:
(1) 656mg of 2-methylimidazole and 297mg of zinc nitrate hexahydrate are dissolved in 4.5mL of methanol respectively;
(2) Taking 367mg of lead bromide and 112mg of methylamine bromide, adding 1mLN of lead bromide, N-dimethylformamide and 200 mu L of oleylamine in sequence, and stirring;
(3) Sequentially adding the methanol solution of 2-methylimidazole in the step (1) and the methanol solution of zinc nitrate hexahydrate in the step (2), and violently stirring at room temperature for 1h to obtain a precursor solution of MP QDs;
(4) Standing the precursor solution, removing the solvent, adding 10mL of toluene, dissolving and stirring for 3h; the solution color gradually changes from white to light orange during stirring;
(5) And centrifuging the stirred solution to obtain a precipitate, washing the precipitate by adopting N, N-dimethylformamide and ethanol, and drying to obtain the ZIF-8 coated MP QDs composite material.
Preferably, in the step (1), 2-methylimidazole and zinc nitrate hexahydrate are respectively dispersed in the methanol solution by using ultrasound.
Preferably, in the step (5), the precipitate is obtained by centrifuging for 5min at the rotating speed of 8000 rpm; and after washing, vacuum drying for 1h at 120 ℃ to obtain solid powder of the ZIF-8 coated MP QDs composite material.
Referring to the attached figure 2, the MP QDs @ ZIF-8 composite material prepared by the method disclosed by the embodiment of the invention is a rhombic dodecahedron, and the edge of the shell has a certain thickness; meanwhile, a ZIF-8 frame can be observed to wrap a plurality of MP QDs with uniform particle size, and the average particle size of the MP QDs is 5.3nm;
referring to FIG. 3, it is shown that the MP QDs @ ZIF-8 composite material prepared by the method of the present invention has a clear lattice spacing of about 0.29nm, which corresponds to the (200) crystal plane of cubic phase MP QDs having a Pm-3m space group, indicating the successful synthesis of the MP QDs @ ZIF-8 composite material of the present invention.
Referring to the attached figure 4, the embodiment of the invention also provides application of the ZIF-8 coated MP QDs composite material to aflatoxin B 1 A method of concentration comprising the steps of:
(1) The ZIF-8 coated MP QDs composite material is adopted to prepare the aflatoxin B 1 Molecularly imprinted electrochemiluminescence sensors (MIP/MP QDs @ ZIF-8/GCE);
(2) Constructing a three-electrode system by using the glassy carbon electrode modified by the ZIF-8 coated MP QDs composite material as a working electrode, a platinum wire as an auxiliary electrode and Ag/AgCl as a reference electrode, placing the three electrodes in an electrolytic cell containing electrolyte, and connecting the three electrodes with an electrochemical luminoscope; the electrolyte is a PBS solution containing 0.01moL/L co-reactant TPA and 0.1moL/L, and the pH value is 7.4; the photomultiplier of the electrochemical luminometer is 800V, the amplification level is 4, the potential scanning range is 0-1.5V, and the scanning speed is 200mV/s;
(3) Detection of elution and adsorption by electrochemiluminescence 5X 10 -6 、5×10 -5 、5×10 -4 、5×10 -3 、5×10 -2 0.5, 1, 10 and 20ng/mL series concentration of aflatoxin B 1 The electrochemical luminescence signals of the MIP/MP QDs @ ZIF-8/GCE sensor are respectively marked as I ECL0 、I ECLn (n＝1、2、3…n)；
(4) Establishment of I ECL0 、I ECLn Difference of (a) with aflatoxin B 1 The quantitative relation of the concentration is formula (1);
ΔI ECL ＝743.9 lg c+4662(R 2 ＝0.999) (1)
wherein c is aflatoxin B 1 ng/mL; delta I ECL For adsorbing the electrochemical luminescence signal and I of the MIP/MP QDs @ ZIF-8/GCE sensor of the sample solution ECL0 A difference of (d); the detection limit is 3.5fg/mL;
(5) Detecting the electrochemical luminescence signal of MIP/MP QDs @ ZIF-8/GCE sensor for adsorbing the sample solution by an electrochemical luminometer, and obtaining the aflatoxin B in the sample according to the quantitative relation 1 The concentration of (2).
In the embodiment of the invention, AFB with different concentrations is added into the pre-treated corn diluted extract 1 (20.0 ng/mL, 10.0ng/mL and 1.0 ng/mL) were subjected to recovery detection, and the detection concentration was obtained according to the formula (1). The recovery test data are shown in table 1.
Table 1 addition mark recovery experiment result of detecting aflatoxin B1 concentration in food by electrochemical luminescence sensor prepared from composite material prepared by the method of the first embodiment of the present invention
As can be seen from Table 1, the recovery rates of the added standard are 107.0%, 106.0% and 107.0%, respectively, and the relative standard deviation is between 4.8% and 7.1%, which indicates that the aflatoxin B prepared from the ZIF-8-coated MP QDs composite material of the embodiment of the invention 1 The molecularly imprinted electrochemiluminescence sensor can be applied to AFB in corn samples 1 The detection is analyzed, the detection sensitivity is high, and the result accuracy is good.
Preferably, in the step (1), the method for preparing the aflatoxin B1 molecular imprinting electrochemical luminescence sensor comprises the following steps:
(11) Pretreating a Glassy Carbon Electrode (GCE); polishing the GCE electrode on polishing cloth scattered with 0.3 μm and 0.05 μm aluminum oxide powder, and washing the GCE surface with ultrapure water; then sequentially using ultrapure water, absolute ethyl alcohol and ultrapure water to carry out ultrasonic cleaning treatment on the polished GCE for 10min respectively, and naturally drying at room temperature;
(12) Dispersing 2mg of prepared ZIF-8 coated MP QDs composite material into 200 mu L of ultrapure water, performing ultrasonic dispersion to obtain a composite material solution, transferring 3 mu L of the composite material solution to vertically drip-coat the surface of the GCE pretreated in the step (1), and naturally drying under a dark condition to form an MP QDs @ ZIF-8/GCE electrochemical luminescence sensor;
(13) Mixing methacrylic acid (MAA), ethylene glycol dimethacrylate (EDMA), azobisisobutyronitrile (AIBN) with a concentration of 10 -5 mol/L template molecule AFB 1 Mixing, vortexing sufficiently, dripping 3 μ L of the mixture on the surface of the electrochemical luminescence sensor obtained in step (2), and immediately irradiating under 365nm ultraviolet light for 10min to obtain AFB 1 Imprinted ECL sensors (MIP/MP QDs @ ZIF-8/GCE).
MIP/MP QDs @ ZIF-8/GCE prepared in the embodiment of the invention is put in an EP tube containing absolute ethyl alcohol for elution for 5min, then the surface is washed, and ECL signals are measured and recorded by an electrochemical luminometer to form a curve b.
Soaking the eluted sensor in the solution with the concentration of 01pg/mL AFB 1 And culturing in the solution for 10min, taking out, washing the surface with absolute ethyl alcohol, and measuring and recording corresponding ECL signals by an electrochemical luminometer to form a curve c.
The embodiment of the invention also records the sensor signal of the polymer film which is imprinted to be dense and non-conductive, and forms a curve a.
Referring to the attached figure 5, after the MIP/MP QDs @ ZIF-8/GCE electrochemiluminescence sensor prepared by the embodiment of the invention is eluted by absolute ethyl alcohol, the template molecules are effectively removed, so that sites for electron transfer are left, and a sharply increased signal appears on a curve b; soaking the eluted sensor in the AFB containing the target object 1 The eluted cavity and AFB are cultured in the solution 1 Specific binding occurred and the ECL response was significantly diminished. Shows that the successful construction of the ZIF-8 coated MP QDs composite material electrochemical luminescence sensor prepared by the method is applied to the target AFB 1 The molecule has the capability of specific recognition and can be effectively applied to detecting AFB 1 The concentration of (2).
Comparative example 1
The invention also provides a preparation method of the single perovskite quantum dot (MP QDs) material, which comprises the following steps:
(1) 367mg of PbBr was weighed 2 And 112mg of CH 3 NH 3 Placing Br in a round-bottom flask, adding 1mLDMF and 200 mu L oleylamine in sequence, and rapidly stirring to dissolve the raw materials;
(2) Injecting 10mL of toluene into the step (1), and stirring for 3h; the solution gradually changed from white to dark orange during stirring;
(3) Centrifuging the reacted solution at 8000rpm for 5min, collecting precipitate, washing with DMF and ethanol for several times, and vacuum drying at 120 deg.C for 1 hr to obtain solid powder.
Referring to fig. 6, it is shown that the shape of single perovskite quantum dot (MP QDs) materials is different from the composite materials prepared by the embodiments of the present invention.
Referring to the attached figure 7, the MP QDs @ ZIF-8 composite material prepared by the embodiment of the invention and the material of the comparative example are subjected to electrochemical luminescence sensing analysis and detection. The corresponding ECL signal stability of the MP QDs @ ZIF-8 composite material prepared by the embodiment of the invention in a water environment is high, and the signal of single MP QDs shows a gradual attenuation trend and has a high attenuation speed. The ZIF-8 is shown to have excellent coating capability, and MP QDs are prevented from dissolving in a water environment, so that the water stability of the MP QDs @ ZIF-8 composite material prepared by the embodiment of the invention is greatly improved.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (10)
1. A preparation method of a ZIF-8 coating-based composite material is characterized by comprising the following steps:
(1) Taking a proper amount of 2-methylimidazole and zinc nitrate hexahydrate, and respectively dissolving in methanol;
(2) Taking a proper amount of lead bromide and methylamine bromide, adding N, N-dimethylformamide and oleylamine, and stirring;
(3) Sequentially adding the methanol solution of 2-methylimidazole in the step (1) and the methanol solution of zinc nitrate hexahydrate in the step (2), and violently stirring at room temperature to obtain a precursor solution of MP QDs;
(4) Standing the precursor solution, removing the solvent, adding a proper amount of toluene, dissolving and stirring until the reaction is finished;
(5) And centrifuging the solution after the reaction to obtain a precipitate, washing the precipitate by adopting N, N-dimethylformamide and ethanol, and drying to obtain the ZIF-8 coated MP QDs composite material, namely the MP QDs @ ZIF-8 composite material.
2. The preparation method of the ZIF-8 coating-based composite material as claimed in claim 1, comprising the steps of:
(1) 656mg of 2-methylimidazole and 297mg of zinc nitrate hexahydrate are dissolved in 4.5mL of methanol respectively;
(2) Taking 367mg of lead bromide and 112mg of methylamine bromide, and adding 1mL of N, N-dimethylformamide and 200 mu L of oleylamine sequentially and stirring;
(3) Sequentially adding the methanol solution of 2-methylimidazole in the step (1) and the methanol solution of zinc nitrate hexahydrate in the step (2), and violently stirring at room temperature for 1h to obtain a precursor solution of MP QDs;
(4) Standing the precursor solution, removing the solvent, adding 10mL of toluene, dissolving and stirring for 3h;
(5) And centrifuging the stirred solution to obtain a precipitate, washing the precipitate by adopting N, N-dimethylformamide and ethanol, and drying the precipitate in a vacuum drying oven at the temperature of 120 ℃ for 1 hour to obtain the ZIF-8 coated MP QDs composite material.
3. Application of ZIF-8 coating-based composite material prepared by method according to any one of claims 1 and 2 in detection of aflatoxin B 1 The concentration method is characterized by comprising the following steps:
(1) The ZIF-8 coated MP QDs composite material is adopted to prepare the aflatoxin B 1 Molecularly imprinted electrochemiluminescence sensors (MIP/MP QDs @ ZIF-8/GCE);
(2) Constructing a three-electrode system by using the glassy carbon electrode modified by the ZIF-8 coated MP QDs composite material as a working electrode, a platinum wire as an auxiliary electrode and Ag/AgCl as a reference electrode, placing the three electrodes in an electrolytic cell containing electrolyte, and connecting the three electrodes with an electrochemical luminoscope;
(3) Detecting, eluting and adsorbing a series of aflatoxins B with different concentrations in an electrochemical luminometer 1 The electrochemical luminescence signals of the MIP/MP QDs @ ZIF-8/GCE sensor are respectively marked as I ECL0 、I ECLn (n＝1、2、3···n)；
(4) Establishment of I ECL0 、I ECLn Difference of (a) and aflatoxin B 1 A quantitative relationship of concentration;
(5) Detecting the electrochemical luminescence signal of MIP/MP QDs @ ZIF-8/GCE sensor for adsorbing the sample solution by an electrochemical luminometer, and obtaining the aflatoxin B in the sample according to the quantitative relation 1 The concentration of (c).
4. The ZIF-based of claim 3Application of-8 coated composite material to detection of aflatoxin B 1 A method of concentration characterized by; in the step (1), aflatoxin B is prepared 1 A method of molecularly imprinted electrochemiluminescence sensors (MIP/MP QDs @ ZIF-8/GCE) comprising the steps of:
(11) Pretreating a Glassy Carbon Electrode (GCE);
(12) Modifying the prepared ZIF-8 coated MP QDs composite material solution on the surface of the pretreated glassy carbon electrode, and drying to form an MP QDs @ ZIF-8/GCE electrochemical luminescence sensor;
(13) Will contain the active component at a concentration of 10 -5 mol/L template molecule aflatoxin B 1 The molecular imprinting mixed solution is modified on the MP QDs @ ZIF-8/GCE electrochemical luminescence sensor, and then a layer of uniform and compact polymer film is formed through photopolymerization, so that the aflatoxin B based on the ZIF-8 coated MP QDs composite material is obtained 1 A molecular imprinting electrochemical luminescence sensor (MIP/MP QDs @ ZIF-8/GCE).
5. The ZIF-8 coating-based composite material applied to detecting aflatoxin B according to claim 3 1 The concentration method is characterized in that in the step (2), the electrolyte is a PBS solution containing 0.01moL/L of co-reactant TPA and 0.1moL/L, and the pH value is 7.4; the photomultiplier of the electrochemical luminometer is 800V, the amplification level is 4, the potential scanning range is 0-1.5V, and the scanning speed is 200mV/s.
6. The ZIF-8 coating-based composite material applied to detecting aflatoxin B according to claim 3 1 A method of concentration characterized by; in the step (3), the elution and the adsorption are detected by an electrochemical luminometer, and the detection is carried out at 5 multiplied by 10 -6 、5×10 -5 、5×10 -4 、5×10 -3 、5×10 -2 0.5, 1, 10 and 20ng/mL series concentration of aflatoxin B 1 The electrochemical luminescence signals of the MIP/MP QDs @ ZIF-8/GCE sensor are respectively marked as I ECL0 、I ECLn (n＝1、2、3…n)。
7. The base of claim 6Application of composite material coated by ZIF-8 in detection of aflatoxin B 1 A method of concentration characterized by; in the step (4), I is established ECL0 、I ECLn Difference of (a) with aflatoxin B 1 The quantitative relation of the concentration is formula (1);
ΔI ECL ＝743.9lgc+4662(R 2 ＝0.999) (1)
wherein c is aflatoxin B 1 ng/mL; delta I ECL After absorbing sample solution, the electrochemical luminescence signal and I of the MIP/MP QDs @ ZIF-8/GCE sensor ECL0 A difference of (d);
the detection limit of the formula (1) is 3.5fg/mL.
8. The ZIF-8 coating-based composite material of claim 4, used for detecting aflatoxin B 1 The concentration method is characterized in that in the step (12), the ZIF-8 coated MP QDs composite material is dissolved in water to obtain a composite material solution.
9. The ZIF-8 coating based composite material of claim 4 used for detecting aflatoxin B 1 The concentration method is characterized in that in the step (13), the molecularly imprinted mixed solution containing the template molecule is prepared from template molecule aflatoxin B 1 And a molecularly imprinted polymeric solution.
10. The ZIF-8 coating-based composite material of claim 4, used for detecting aflatoxin B 1 The concentration method is characterized in that in the step (13), the molecularly imprinted mixed solution containing the template molecule is prepared from template molecule aflatoxin B 1 And methacrylic acid, ethylene glycol dimethacrylate and azobisisobutyronitrile.
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