CN112730561B - Electrochemical biosensor based on supermolecule host-guest recognition technology and preparation method and application thereof - Google Patents
Electrochemical biosensor based on supermolecule host-guest recognition technology and preparation method and application thereof Download PDFInfo
- Publication number
- CN112730561B CN112730561B CN202011500136.0A CN202011500136A CN112730561B CN 112730561 B CN112730561 B CN 112730561B CN 202011500136 A CN202011500136 A CN 202011500136A CN 112730561 B CN112730561 B CN 112730561B
- Authority
- CN
- China
- Prior art keywords
- zif
- solution
- aunps
- psc
- glassy carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The application belongs to the technical field of sensors, and particularly relates to an electrochemical biosensor based on a supramolecular guest-host recognition technology, and a preparation method and application thereof. The electrochemical biosensor comprises modified nanoparticles and ZIF-8 metalA frame; the modified nano particles are compounded with a ZIF-8 metal organic framework; the modified nano particle is 4-sulfonyl cup [4 ]]Aromatic hydrocarbon pSC 4 Coating the periphery of the metal nano particles. The application also provides a preparation method: mixing a zinc source, dimethyl imidazole and a solvent to obtain a ZIF-8 solution; mixing the modified nano particle solution and the ZIF-8 solution, and centrifuging to obtain a precipitate, wherein the precipitate is an electrochemical biosensor based on a supramolecular guest-host recognition technology; the modified nano particle solution is 4-sulfonyl cup [4 ]]Aromatic hydrocarbon pSC 4 And a complex solution of metal nanoparticles. The electrochemical biosensor can improve the sensitivity and specificity of detecting small molecular substances.
Description
Technical Field
The application belongs to the technical field of sensors, and particularly relates to an electrochemical biosensor based on a supramolecular host-guest recognition technology, and a preparation method and application thereof.
Background
Small molecule substance Paraquat (PQ), PQ, is used as a non-selective organic heterocyclic herbicide. Mainly acts on a chloroplast envelope membrane of a green plant, can induce the chloroplast envelope membrane to generate excessive active oxygen, and exerts the weeding effect of the chloroplast envelope membrane by damaging the structure of the plant envelope membrane. The herbicide has the advantages of low price, reliable and quick weeding effect, quick inactivation after contacting soil and relatively small harm to the environment, so the herbicide is widely applied to agricultural production all over the world. However, PQ is extremely toxic to human and mammals, and the current reports on PQ poisoning are rare, and are concerned about the high fatality rate and the annual increasing trend of the incidence rate. Currently, in practical applications, a large-scale analyzer or a simple kit is mainly used for detecting small-molecule substances such as PQ.
However, in the process of detecting small molecular substances by using the existing method, a series of problems can be caused, such as high cost of a large-scale analytical instrument, long experiment pretreatment period, high detection limit, complex operation and long consumed time; the simple and convenient kit detection method has the problems of insufficient detection precision, short shelf life, easy occurrence of false positive and the like. Therefore, there is an urgent need for a simple, rapid, sensitive, and stable substance and method for detecting small molecules.
Disclosure of Invention
In view of the above, the present application provides an electrochemical biosensor based on a supramolecular host-guest recognition technology, a preparation method thereof, and an application thereof, wherein the electrochemical biosensor is used for detecting small molecular substances based on host-guest recognition and an electrochemical technology, and can improve the sensitivity and specificity of detecting the small molecular substances.
The application provides an electrochemical biosensor based on a supermolecular host-guest recognition technology in a first aspect, which comprises: modified nanoparticles and a ZIF-8 metal organic framework;
the modified nano-particles are compounded with the ZIF-8 metal organic framework;
the modified nano particle is 4-sulfonyl cup [4 ]]Aromatic hydrocarbon pSC 4 Coating the periphery of the metal nano particles.
Specifically, ZIF-8 (Zn (Hmim) 2 Hmim = 2-methylimidazole) belongs to zeolitic imidazolate framework materials.
In another embodiment, the metal nanoparticles are selected from one or more of nanogold, nanosilver, gold nanorods, gold nanoclusters, silver nanorods, and silver gold nanoclusters.
In another embodiment, the metal nanoparticles are nanogold.
In a second aspect, the present application provides a method for preparing the electrochemical biosensor, comprising the steps of:
Specifically, the pSC is prepared by adopting a one-step method 4 -AuNPs @ ZIF-8 electrochemical biosensor.
Specifically, the step 2 specifically comprises adding pSC in the process of mixing the zinc source, the dimethyl imidazole and the solvent while stirring 4 AuNPs, when the solution turns from colorless to light red, adding zinc source solution, stirring and mixing, and centrifuging to obtain redColor precipitation, discarding supernatant to obtain pSC 4 -AuNPs@ZIF-8。
In another embodiment, in step 1, the zinc source is selected from Zn (OH) 2 Or Zn (NO) 3 ) 2 ·6H 2 O、ZnCl 2 And ZnSO 4 One or more of (a).
In another embodiment, in step 1, the zinc source is Zn (NO) 3 ) 2 ·6H 2 O; 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water, and sonication was carried out for 20min until the solution was completely dissolved, thereby obtaining a 4.22791mg/mL of ZIF-8 solution.
In another embodiment, in step 1, the solvent is selected from water.
Specifically, in step 1, the water may be one or more of deionized water, purified water, distilled water and ultrapure water.
In another embodiment, in the step 2, the ratio of the modified nanoparticle solution to the ZIF-8 solution is (2-10): 44.
in another embodiment, in step 2, the concentration of the gold nanoparticles in the modified nanoparticle solution is: 2.63X 10 -2 mol/L; the ZIF-8 solution is 4.22791mg/mL.
In another embodiment, in step 2, the method for preparing the modified nanoparticle solution comprises: mixing water and HAuCl 4 Solution, pSC 4 Mixing the solution to obtain a mixed solution, and then adding NaBH 4 And mixing the solution with the mixed solution to prepare the modified nano particle solution.
In another embodiment, in step 2, the modified nanoparticle solution is HAuCl 4 The concentration of the solution is 2.63X 10 -2 mol/L，pSC 4 The solution is 10 -2 mol/L。
Specifically, the preparation method of the modified nanoparticle solution comprises the step of putting 94mL of deionized water into a three-neck flask. Then, 2mL of HAuCl 4 Solution (2.63X 10) -2 mol/L) and 2mL of pSC 4 Solution (10) -2 mol/mL) was charged into the flask and stirred vigorously at room temperature for 20 minutes. (make it possible toThe whole liquid level is rotated, no special rotating speed requirement) to prepare the newly prepared NaBH 4 Solution (10- 2 mol/mL) was quickly injected into the bottle. For subsequent use.
In another embodiment, step 2 specifically includes: 4.4mL of 4.22791mg/mL ZIF-8 solution was added to 1mL of pSC with stirring 4 -AuNPs solutions; then adding 0.4mL and 0.77218mg/mL zinc nitrate solution, and continuing stirring for 10min to prepare the electrochemical biosensor pSC based on the supermolecule host-guest recognition technology 4 -AuNPs @ ZIF-8 solution.
In another embodiment, step 2 is followed by a purification process comprising: and (3) re-dissolving the electrochemical biosensor based on the supermolecule host-guest recognition technology, centrifuging, and repeating for 1-3 times to obtain the electrochemical biosensor based on the supermolecule host-guest recognition technology.
Specifically, the purification treatment comprises: and (3) carrying out redissolution and centrifugation treatment on the electrochemical biosensor by adopting the solution prepared by the electrochemical biosensor based on the supermolecule host-guest recognition technology, and repeating for 1-3 times to obtain the high-purity electrochemical biosensor. The solution prepared by the electrochemical biosensor based on the supermolecule host-guest recognition technology is water.
Specifically, the purification specifically comprises: subjecting the pSC obtained in the step 2 to 4 -AuNPs @ ZIF-8 is redissolved in water with the same volume, then the centrifugal redissolution treatment is carried out again, the process is repeated for 1 to 3 times, and high-purity pSC is obtained 4 -AuNPs@ZIF-8。
The third aspect of the application discloses the application of the electrochemical biosensor prepared by the preparation method of the electrochemical biosensor in detecting small molecular substances.
In particular, the present application utilizes pSC 4 AuNPs @ ZIF-8 detects trace contaminants PQ in sample water using a sensitive electrochemical technique.
In another embodiment, the small molecule substance is selected from one of paraquat, acetamiprid, isoproturon, or basic malachite green.
In another embodiment, the detecting of the application comprises:
1. soaking a glassy carbon electrode in pSC 4 AuNPs @ ZIF-8 solution, allowing pSC to grow 4 AuNPs @ ZIF-8 is attached to the surface of a glassy carbon electrode.
2. PQ was added dropwise to the pSC to which the above-mentioned pSC was attached 4 And (3) treating the surface of the glassy carbon electrode of AuNPs @ ZIF-8 for 10-50 min to obtain the PQ-treated glassy carbon electrode.
3. And (3) putting the PQ-treated glassy carbon electrode into an electrolyte to measure the electrochemical impedance change of a three-electrode system.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, and the working electrode comprises: the liquid to be detected of the PQ-treated glassy carbon electrode is used as electrolyte; electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide with pH value of 5-9 is used as electrolyte for experimental detection.
Wherein the detection volume of the PQ is 5-25 mu L, and the detection concentration of the PQ is 1 pM-10 nM; PQ was added dropwise to the pSC attached thereto 4 The treatment time on the surface of the glassy carbon electrode of-AuNPs @ ZIF-8 is 10-50 min; the electrolyte is PBS buffer solution with pH value of 5-9 and containing 5mM potassium ferricyanide.
Based on the data of the embodiment of the application, the application can pass through the 4-sulfonyl cup [4 ] with good water solubility]Aromatic hydrocarbons (pSC) 4 ) Due to the binding of the hydroxyl terminus of pSC to ZIF-8 4 The cup-shaped cavity performs host-guest recognition to aggregate AuNPs, thereby capturing PQ through recognition, and pSC mediated by ZIF-8 in vitro 4 AuNPs aggregate to form a nano-complex, and specificity is realized through guest-host recognition, so that the amplification of electrochemical signals is realized. ZIF-8 and pSC compared to bare electrode 4 The peak of the-AuNPs @ ZIF-8 modified electrode is reduced because ZIF-8 may hinder electron transfer. pSC 4 The current of AuNPs @ ZIF-8 is greater than that of ZIF-8 because of pSC 4 AuNPs can provide greater electrochemically accelerated electron transfer. On the other hand, upon interaction of the ZIF-8 modified electrode with PQ, the redox peak current increases due to the pi-pi conjugation effect of adsorbed PQ. pSC (pSC) 4 -AuNPs @ ZIF-8 modified electrode andafter PQ interaction, the redox peak current decreases. Experiments in the examples of the present application demonstrated that the presence of ZIF-8 (physisorption) and pSC 4 AuNPs @ ZIF-8 (PQ and pSC) 4 Host-guest interactions between) modify the adsorption differences on the electrodes. As the steric hindrance can be seriously increased by ZIF-8, the electron transfer in an electrode interface is seriously inhibited, and more pSCs are generated along with the increase of the concentration of small molecular substances such as PQ and the like 4 AuNPs will bond to the surface of glassy carbon electrodes, multilayer pSC 4 Modification of AuNPs @ ZIF-8 can recruit more small molecules to achieve a stronger EIS signal response, resulting in a significant amplification of the EIS response signal. By the design of the application, 4-sulfonyl cup [4 ]]Arene-modified gold nanoparticles (pSC) 4 AuNPs) and MOFs, and the electrochemical method is adopted to detect small molecular substances such as PQ and the like, and the electrochemical method is adopted to detect the small molecules, so that the sensitivity and specificity of detection are greatly improved.
Compared with the prior art:
this application utilizes a 4-sulfonyl cup [4 ]]Arene-modified gold nanoparticles (pSC) 4 AuNPs) and ZIF-8, and a novel porous sulfonated calixarene coated gold nanoparticle functionalized metal organic framework (pSC) is synthesized 4 AuNPs @ ZIF-8), pSC of the present application 4 -AuNPs @ ZIF-8 due to pSC 4 The detection method has the advantages that the detection cost is low, the time is short, the operation is simple and convenient, and high specificity and sensitivity are realized. The application creatively constructs the sensitive PQ sensor, and effectively improves the sensitivity and specificity of the sensor.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows pSC provided in the examples of the present application 4 -TEM atlas at aunps @ zif-8; a is 4-sulfonyl cup [4 ]]Aromatic hydrocarbon pSC 4 Coated on metal nanoparticlesTEM image of a peripherally modified nanoparticle, B is pSC 4 TEM image of AuNPs @ ZIF-8;
FIG. 2 is a pSC provided in the examples of the present application 4 Electrochemical impedance spectroscopy EIS and cyclic voltammetry CV results of AuNPs @ ZIF-8;
FIG. 3 is a test of the effect of various factors on PQ detection provided in the examples of the present application;
FIG. 4 shows pSC provided in the examples of the present application 4 -AuNPs @ ZIF-8PQ concentration range test and test for detecting different small molecule substances.
Detailed Description
The application provides an electrochemical biosensor based on a supramolecular host-guest recognition technology, and a preparation method and application thereof, which are used for solving the technical defects of high cost, long experiment pretreatment period, high detection limit, complex operation and long consumed time in the prior art for detecting small molecular substances.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Wherein, the reagents or raw materials used in the following examples are all sold in the market or made by the user; pure ZIF-8 solutions and ZIF-8 powders used in the following examples were prepared by dissolving 117mg of zinc nitrate in 0.8mL of deionized water, dissolving 22.7g of 2-methylimidazole in 80mL of deionized water, and then sonicating the solutions at 42kw for 20min using an ultrasonic cleaning apparatus. After ultrasonic treatment, centrifuging by a high-speed centrifuge (9500rpm 10min 26 ℃) to obtain white precipitate, removing supernatant, adding ultrapure water with the same volume for redissolving, centrifuging for 3 times, putting the obtained ZIF-8 solution at 80 ℃ for vacuum drying for 2h to obtain ZIF-8 powder, and storing at 4 ℃.
pSC 4 The preparation method of the AuNPs solution comprises the following steps: 94mL of deionized water was first placed in a three-neck flask. Then, 2mLHAuCl was added 4 Solution (2.63X 10) -2 mol/mL) and 2mLpSC 4 Solution (10) -2 mol/L) was poured into the flask and stirred vigorously at room temperature for 20 minutes. (the whole liquid level is rotated, no special rotating speed requirement is needed) the newly prepared NaBH is added 4 Solution (10) - 2 mol/mL) was quickly injected into the bottle. For subsequent experiments, the concentration of the gold nanoparticles is as follows: 2.63X 10 -2 mol/L。
Electrochemical biosensor label of the present application based on supramolecular host-guest recognition technology is pSC 4 -AuNPs @ ZIF-8, modified nanoparticle solution is pSC 4 -AuNPs solutions.
Example 1
The embodiment of the application provides pSC 4 -AuNPs @ ZIF-8 preparation method and electrochemical determination test thereof, including:
(1)pSC 4 -preparation of aunps @ zif-8: first, 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and sonicated for 20min until all dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
4.4mL of the ZIF-8 solution was then added to 1mL of pSC with stirring 4 AuNPs solution, changing from colorless to light red, then adding prepared 0.4mL,0.77218mg/mL zinc nitrate solution, and continuing stirring for 10min to obtain pSC 4 -AuNPs @ ZIF-8 solution. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs @ ZIF-8 was stored at 4 ℃.
For pSC of the examples of the present application 4 -AuNPs @ ZIF-8 for DLS and TEM analysis, pSC of the examples of the present application 4 The TEM pattern of-AuNPs @ ZIF-8 is shown in FIG. 1. The pSCs obtained in the examples of the present application were characterized by Dynamic Light Scattering (DLS), zeta potential and Transmission Electron Microscopy (TEM) 4 AuNPs @ ZIF-8. It can be found that the gold nanoparticles are red-shifted in peak position before and after the ZIF-8 modification. The embodiments of the present application were successfully madePrepared pSC 4 -AuNPs@ZIF-8。
(2) Electrochemical impedance spectroscopy and cyclic voltammetry tests: bare glass carbon electrodes (labeled as barrel GCE in FIGS. 2A and 2B), pSC attached with the above procedure, respectively 4 Glassy carbon electrode of AuNPs @ ZIF-8 (pSC with glassy carbon electrode soaked in the above-mentioned step) 4 -AuNPs @ ZIF-8 solution, FIG. 2A and FIG. 2B labeled pSC 4 AuNPs @ ZIF-8) electrochemical impedance spectroscopy EIS and cyclic voltammetry CV testing, and attaching 1pM of PQ-treated to pSC 4 Glassy carbon electrode of AuNPs @ ZIF-8 (PQ treatment of 1pM pSC to which the above-described procedure was attached 4 -glassy carbon electrode of AuNPs @ ZIF-8 for 40min, labeled 1pM in FIGS. 2A and 2B) was subjected to EIS test and cyclic voltammetry CV, the results are shown in FIG. 2, FIG. 2A is Bare GCE, pSC 4 EIS curves for AuNPs @ ZIF-8 and 1pM, FIG. 2B Bar GCE, pSC 4 CV curves of AuNPs @ ZIF-8 and 1pM, it can be seen that pSC prepared herein 4 AuNPs @ ZIF-8 can detect PQ by electrochemical methods.
Example 2
The present embodiments provide different pscs 4 -aunps @ zif-8 and assays for its detection of PQ, including:
1. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water, and sonication was carried out for 20min until all the solution was dissolved, to obtain a 4.4mL,4.22791mg/mL ZIF-8 solution.
Then, 4.4mL of the ZIF-8 solution was added to 1000. Mu.L of pSC with stirring 4 AuNPs solution, changing from colorless to light red. A prepared 0.4mL,0.77218mg/mL zinc nitrate solution was then added with stirring. Stirring for 10min to obtain pSC 4 -AuNPs @ ZIF-8 solution. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs-1@ZIF-8。
2. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water, and 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and subjected to ultrasonic treatment for 20min until all the solution was dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
Then, 4.4mL of the ZIF-8 solution was added to 800. Mu.L of pSC with stirring 4 AuNPs solution, changing from colorless to light red. While stirring, a prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added thereto, and stirring was continued for 10min to obtain pSC 4 -AuNPs @ ZIF-8 solution. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs-2@ZIF-8。
3. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water, and sonication was carried out for 20min until all the solution was dissolved, to obtain a 4.4mL,4.22791mg/mL ZIF-8 solution.
4.4mL of the ZIF-8 solution was then added to 600. Mu.L of pSC with stirring 4 AuNPs solution, changing from colorless to light red. While stirring, the prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added and stirring was continued for 10min. Loading the same amount of above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolution, centrifuging for 3 times, and collecting pSC 4 -AuNPs-3@ZIF-8。
4. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water, and sonication was carried out for 20min until all the solution was dissolved, to obtain a 4.4mL,4.22791mg/mL ZIF-8 solution.
4.4mL of the ZIF-8 solution was then added to 400. Mu.L of pSC with stirring 4 AuNPs solution, changing from colorless to light red. With stirring, a prepared 0.4mL,0.77218mg/mL zinc nitrate solution was then added and stirring continued for 10min. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs-4@ZIF-8。
5. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water, and 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and subjected to ultrasonic treatment for 20min until all the solution was dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
Then, 4.4mL of the ZIF-8 solution was added to 200. Mu.L of pSC with stirring 4 AuNPs solution, changing from colorless to light red. While stirring, the prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added and stirring was continued for 10min. Loading the same amount of above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolution, centrifuging for 3 times, and collecting pSC 4 -AuNPs-5@ZIF-8。
6. The pSC prepared above was used 4 -AuNPs-1@ZIF-8、pSC 4 -AuNPs-2@ZIF-8、pSC 4 -AuNPs-3@ZIF-8、pSC 4 -AuNPs-4@ ZIF-8 and pSC 4 AuNPs-5@ ZIF-8 was dissolved in water to prepare five 2.83mg/mL solutions. Then, soaking a glassy carbon electrode in the pSC alone 4 -AuNPs-1@ZIF-8、pSC 4 -AuNPs-2@ZIF-8、pSC 4 -AuNPs-3@ZIF-8、pSC 4 -AuNPs-4@ ZIF-8 and pSC 4 In the-AuNPs-5 @ ZIF-8 solution, 5 glassy carbon electrodes are parallel, 5 glassy carbon electrodes are soaked in the same solution to obtain 25 glassy carbon electrodes in total so as to avoid large errors of electrochemical detection data and enable pSC (plasma sensitive carbon) to be realized 4 -AuNPs-1@ZIF-8、pSC 4 -AuNPs-2@ZIF-8、pSC 4 -AuNPs-3@ZIF-8、pSC 4 -AuNPs-4@ ZIF-8 and pSC 4 AuNPs-5@ ZIF-8 is separately attached to a glassy carbon electrode.
7. 20 μ L of 1nM PQ was added dropwise to each of the five pSCs attached thereto 4 The surface of the glassy carbon electrode of AuNPs @ ZIF-8 was treated for 40min to obtain a PQ-treated glassy carbon electrode, and the PQ-treated glassy carbon electrode was placed in an electrolyte to measure the electrochemical impedance change, and the results are shown in FIG. 3A, and it is clear from FIG. 3A that pSC of the present invention 4 -AuNPs @ ZIF-8 preparation method in pSC 4 The feeding amount of the AuNPs solution is 200-1000 mu L, and the optimal feeding amount is1000μL。
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode comprises: the liquid to be detected of the PQ-treated glassy carbon electrode is used as electrolyte; electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH 7.4 was used as electrolyte for the experimental examination.
Example 3
The embodiment of the application provides a test for the influence of different PQ dropping amounts on PQ detection, which comprises the following steps:
1. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and sonicated for 20min until all dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
Then, 4.4mL of ZIF-8 solution was added to 1000. Mu.L of pSC with stirring at room temperature 4 AuNPs solution, changing from colorless to light red. While stirring, the prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added and stirring was continued for 10min. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs-1@ZIF-8。
2. pSC prepared as described above 4 AuNPs-1@ ZIF-8 was dissolved in water to give a solution of 2.83 mg/mL. Then, 25 glassy carbon electrodes were separately immersed in the above pSC 4 AuNPs-1@ ZIF-8 solution, allowing pSC 4 AuNPs-1@ ZIF-8 is separately attached to a glassy carbon electrode.
3. mu.L of 1nM PQ was added dropwise to each of the 5 pSCs 4 Carrying out surface treatment on a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode-1; mu.L of 1nM PQ was added dropwise to each of the 5 pSCs adhered thereto 4 Carrying out surface treatment on a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode-2; 15 μ L of 1nM PQ was added dropwise to each of the 5 pSCs 4 -AuNPs @ ZIF-8 glassy carbon electrode tablePerforming surface treatment for 40min to obtain a PQ-treated glassy carbon electrode-3; mu.L of 1nM PQ was added dropwise to each of the 5 pSCs 4 Carrying out surface treatment on a glassy carbon electrode of-AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode-4; 25 μ L of 1nM PQ was added dropwise to each of the 5 pSCs 4 After the surface of the glassy carbon electrode of AuNPs @ ZIF-8 is treated for 40min, the obtained PQ-treated glassy carbon electrodes-5,5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. The five PQ-treated glassy carbon electrodes were placed in an electrolyte and subjected to electrochemical impedance change measurement, and the results are shown in fig. 3B, and it can be seen from fig. 3B that pSC of the present application 4 The dosage of PQ dropwise added on a glassy carbon electrode in an AuNPs @ ZIF-8 detection PQ system is 5-25 muL, and the optimal dosage is 20 muL.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, and the working electrode comprises: the liquid to be detected of the PQ-treated glassy carbon electrode is used as electrolyte; electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH 7.4 was used as electrolyte for the experimental examination.
Example 4
The embodiment of the application provides a test of the influence of different PQ processing glassy carbon electrode time on PQ detection, which comprises the following steps:
1. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and sonicated for 20min until all dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
4.4mL of ZIF-8 solution was then added to 1000. Mu.L of pSC with stirring at ambient temperature 4 AuNPs solution, changing from colorless to light red. While stirring, the prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added and stirring was continued for 10min. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs-1@ZIF-8。
2. The pSC prepared above was used 4 AuNPs-1@ ZIF-8 was dissolved in water to give a 2.83mg/mL solution. Then, 25 glassy carbon electrodes were separately immersed in the above pSC 4 AuNPs-1@ ZIF-8 solution, allowing pSC 4 AuNPs-1@ ZIF-8 is attached to a glassy carbon electrode alone.
3. mu.L of 1nM PQ was added dropwise to the above 5 pSCs attached thereto 4 Carrying out surface treatment on a glassy carbon electrode of-AuNPs @ ZIF-8 for 10min to obtain a PQ treated glassy carbon electrode-6; mu.L of 1nM PQ was added dropwise to the 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 20min to obtain a PQ-processed glassy carbon electrode-7; mu.L of 1nM PQ was added dropwise to the 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 30min to obtain a PQ-processed glassy carbon electrode-8; mu.L of 1nM PQ was added dropwise to the above 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode-9; mu.L of 1nM PQ was added dropwise to the 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 50min to obtain a PQ-processed glassy carbon electrode-10; 5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. The results of electrochemical impedance change measurements performed by placing the five different volumes of PQ-treated glassy carbon electrodes in an electrolyte are shown in fig. 3C, and it can be seen from fig. 3C that pSC of the present application 4 The time for processing the glassy carbon electrode by PQ in an AuNPs @ ZIF-8 detection PQ system is 10-50 min, and the optimal processing time is 40min.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode comprises: the liquid to be detected of the PQ-treated glassy carbon electrode is used as electrolyte; electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH 7.4 was used as electrolyte for the experimental examination.
Example 5
The embodiment of the application provides a test for influence of different PQ processing glassy carbon electrode time on PQ detection, which comprises the following steps:
1. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and sonicated for 20min until all dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
4.4mL of ZIF-8 solution was then added to 1000. Mu.L of pSC with stirring at ambient temperature 4 AuNPs solution, changing from colorless to light red. While stirring, the prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added and stirring was continued for 10min. Loading the same amount of above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolution, centrifuging for 3 times, and collecting pSC 4 -AuNPs-1@ZIF-8。
2. The pSC prepared above was used 4 AuNPs-1@ ZIF-8 was dissolved in water to give a 2.83mg/mL solution. Then, 25 glassy carbon electrodes were separately immersed in the above pSC 4 AuNPs-1@ ZIF-8 solution, allowing pSC 4 AuNPs-1@ ZIF-8 is attached to a glassy carbon electrode alone.
3. mu.L of 1nM PQ was added dropwise to the 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode; 5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. Placing the five PQ-treated glassy carbon electrodes into an electrolyte (a PBS (phosphate buffered saline) solution with pH value of 5 and containing 5mM potassium ferricyanide) to perform electrochemical impedance change measurement; mu.L of 1nM PQ was added dropwise to the above 5 pSCs attached thereto 4 Treating the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode; 5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. Placing the five PQ-treated glassy carbon electrodes into an electrolyte (a PBS (phosphate buffer solution) with pH value of 6 and containing 5mM potassium ferricyanide) to perform electrochemical impedance change measurement; mu.L of 1nM PQ was added dropwise to the 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode; parallel test with 5 glassy carbon electrodes as a groupTo avoid large errors in electrochemical detection data. Placing the five PQ-treated glassy carbon electrodes into an electrolyte (a PBS (phosphate buffer solution) with pH value of 7 and containing 5mM potassium ferricyanide) to perform electrochemical impedance change measurement; mu.L of 1nM PQ was added dropwise to the 5 pSCs attached thereto 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode; 5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. Placing the five PQ-treated glassy carbon electrodes into an electrolyte (a PBS (phosphate buffer solution) with pH value of 8 and containing 5mM potassium ferricyanide) to carry out electrochemical impedance change measurement; mu.L of 1nM PQ was added dropwise to the above 5 pSCs attached thereto 4 Treating the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode; 5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. The five PQ-treated glassy carbon electrodes were placed in an electrolyte (PBS buffer solution containing 5mM potassium ferricyanide at pH 9) to measure electrochemical impedance changes. Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode comprises: and the liquid to be detected of the PQ-treated glassy carbon electrode is used as an electrolyte. As shown in FIG. 3D, the results of the pSC of the present application are shown in FIG. 3D 4 -AuNPs @ ZIF-8 detects the pH value of the electrolyte in a PQ system to be 5-9, and the optimal pH value is 7min.
Example 6
The embodiment of the application provides pSC 4 -aunps @ zif-8 concentration range assay for detection of PQ comprising:
1. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and sonicated for 20min until all dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
Then, 4.4mL of ZIF-8 solution was added to 1000. Mu.L of pSC with stirring at room temperature 4 AuNPs solution, changing from colorless to light red. While stirring, the prepared 0.4mL,0.77218mg/mL zinc nitrate solution was added and stirring was continued for 10min. Take the same amountThe above solutions were separately put into a centrifuge tube, centrifuged at high speed centrifuge (12000rpm 10min 26 ℃ C.) to obtain red precipitate, the supernatant was removed, then an equal volume of ultrapure water was added to redissolve, centrifuged 3 times, and the pSC was obtained 4 -AuNPs-1@ZIF-8。
2. The pSC prepared above was used 4 AuNPs-1@ ZIF-8 was dissolved in water to give a 2.83mg/mL solution. Then, 15 glassy carbon electrodes were separately immersed in the above pSC 4 AuNPs-1@ ZIF-8 solution, allowing pSC to grow 4 AuNPs-1@ ZIF-8 is attached to a glassy carbon electrode alone.
3. 20. Mu.L of 1pM PQ was added dropwise to the 3 pSCs to which the pSCs were attached 4 Carrying out surface treatment on a glassy carbon electrode of-AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode-11; 20. Mu.L of 10pM PQ was added dropwise to the 3 pSCs to which the pSCs were attached 4 Carrying out surface treatment on a glassy carbon electrode of-AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode-12; 20. Mu.L of 100pM PQ was added dropwise to the 3 pSCs to which the pSCs were attached 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode-13; 20. Mu.L of 1nM PQ was added dropwise to the 3 pSCs to which the above pSCs were attached 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode-14; 20. Mu.L of 10nM PQ was added dropwise to the 3 pSCs to which the above pSCs were attached 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ-processed glassy carbon electrode-15; 3 glassy carbon electrodes are used as a group of parallel tests to avoid larger errors of electrochemical detection data. The five PQ-treated glassy carbon electrodes with different concentrations were placed in an electrolyte solution and subjected to electrochemical impedance change measurement, and the results are shown in fig. 4A, and it can be seen from fig. 4A that pSC of the present application 4 AuNPs @ ZIF-8 detects PQ in the PQ system at a concentration of 1pM to 10nM, showing the relationship between the impedance response and the log of PQ concentration. Detection analysis by three determinations of the mean and SD values of the blank sample gives a linear equation of y =254.1x +690.9 (R) 2 = 0.9939), limit of detection (LOD) 0.00049nM.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, and the working electrode comprises: the liquid to be detected of the PQ-treated glassy carbon electrode is used as electrolyte; electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH 7 was used as electrolyte for the experimental assay.
Example 7
Embodiments of the present application provide pscs 4 -aunps @ zif-8 assays for the detection of different small molecule substances, comprising:
1. 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water. Then, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water and sonicated for 20min until all dissolved, to prepare a 4.4mL,4.22791mg/mL ZIF-8 solution.
4.4mL of ZIF-8 solution was then added to 1000. Mu.L of pSC with stirring at ambient temperature 4 AuNPs solution, changing from colorless to light red. With stirring, a prepared 0.4mL,0.77218mg/mL zinc nitrate solution was then added and stirring continued for 10min. Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolving, centrifuging for 3 times, and collecting pSC 4 -AuNPs-1@ZIF-8。
2. pSC prepared as described above 4 AuNPs-1@ ZIF-8 was dissolved in deionized water to make a 2.38mg/mL solution. Then, 25 glassy carbon electrodes were separately immersed in the above pSC 4 AuNPs-1@ ZIF-8 solution, allowing pSC to grow 4 AuNPs-1@ ZIF-8 is attached to a glassy carbon electrode alone.
3. mu.L of 1nM Paraquat (Paraquat, PQ) was added dropwise to the 5 pSC-attached pSC 4 Treating the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode; mu.L of 10nM Acetamiprid (Acetamiprid) was added dropwise to the 5 pSC attached above 4 Processing the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain the glassy carbon electrode treated by Acetamidoprid; mu.L of 10nM Isoproturon (Isoproturon) was added dropwise to the 5 pSCs attached to the above 4 -AuNPs @ ZIF-8 glassy carbon electrode surface treatment for 40min to obtain Isoproturonon treatmentA rear glassy carbon electrode; mu.L of 10nM Malachite green (basic Malachite green) was added dropwise to the 5 pSC attached above 4 Treating the surface of a glassy carbon electrode of AuNPs @ ZIF-8 for 40min to obtain the glassy carbon electrode treated by Malachite green; 5 glassy carbon electrodes are used as a group of parallel tests to avoid large errors of electrochemical detection data. The results of electrochemical impedance change measurements performed by placing the glassy carbon electrode treated with the five different small molecular substances in an electrolyte are shown in fig. 4B, and it can be seen from fig. 4B that the pSC of the present application 4 AuNPs @ ZIF-8 specifically detects Malachite green, isoproturon, acetaprid and Paraquat, and particularly specifically detects PQ.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, and the working electrode comprises: the liquid to be detected of the PQ-treated glassy carbon electrode is used as electrolyte; electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH 7 was used as electrolyte for the experimental examination.
From the above examples, it can be seen that pSC of the present application was used 4 When AuNPs @ ZIF-8 detects PQ specifically, PQ can pass through pSC 4 And aminomethyl groups, so that the complex can be better combined with the surface of an electrode to achieve the aim of detecting PQ by utilizing the guest recognition effect.
Comparative example 1
Comparative examples of the present application provide control pSCs 4 -aunps @ zif-8 and electrochemical assay tests thereof, comprising:
(1) Control pSC 4 -preparation of aunps @ zif-8: 58.5mg of zinc nitrate was dissolved in 0.4mL of ultrapure water, 1.135g of 2-methylimidazole was dissolved in 4mL of ultrapure water, and sonication was carried out for 20min until all the solution was dissolved, to obtain a 4.4mL,4.22791mg/mL ZIF-8 solution. Then, 1000. Mu.L of ZIF-8 solution was added to 1000. Mu.L of pSC under stirring at room temperature 4 AuNPs solution, changing from colorless to light red. With stirring, a prepared 0.4mL,0.77218mg/mL zinc nitrate solution was then added and stirring continued for 10min. Respectively loading the same amount of the above solutions into centrifuge tubes, and centrifuging with high speed centrifugeHeart (12000rpm 10min 26 deg.C), obtain red precipitate, remove supernatant, add equal volume of ultrapure water for redissolution, centrifuge 3 times, and obtain control pSC 4 -AuNPs-1@ZIF-8。
(2) Electrochemical measurement test: first, a glassy carbon electrode was immersed in the control pSC of the above procedure 4 Control pSC attached to AuNPs @ ZIF-8 solution 4 -a glassy carbon electrode of AuNPs-1@ zif-8; mu.L of 1nM PQ was added dropwise to control pSC attached 4 And (3) treating the surface of a glassy carbon electrode of AuNPs-1@ ZIF-8 for 40min to obtain a PQ treated glassy carbon electrode, and putting the PQ treated glassy carbon electrode into electrolyte for an Electrochemical Impedance Spectroscopy (EIS) test.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, the working electrode is a glassy carbon electrode modified with a metal organic framework structure, and a liquid to be detected is used as an electrolyte. Electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH =7.4 was used as electrolyte for experimental detection.
After repeated experiments, the experimental results show that: after PQ was added, the impedance of PQ dropped rapidly and no amplified signal was generated, and it was found that pSC was prepared 4 When the amount of ZIF-8 fed was too small in the case of AuNPs-1@ ZIF-8, the control pSC was prepared 4 AuNPs-1@ ZIF-8 fails to detect PQ.
Comparative example 2
Comparative examples of the present application provide control pSCs 4 AuNPs @ Cu-MOFs and electrochemical test experiments therefor, pSC 4 The preparation method and the electrochemical test method of the-AuNPs @ Cu-MOFs comprise the following steps:
(1) 0.20g PVP was dissolved in a mixture of 4mL DMF and 4mL ethanol with stirring, and 5.43mg 2-amino terephthalic acid (NH) 2 -BDC) and 24.20mg Cu (NO) 3 ) 2 ·3H 2 O was mixed into 4mL of DMF and added to the mixture. Then 1mL of pSC was added 4 AuNPs solution, changing from colorless to light red.
(2) After the above mixture was sonicated for 20 minutes, it was hydrothermally treated at 100 ℃ for 5 hours in a Teflon-lined reaction vessel, followed by draining the upper liquid, and then 20mL of DMF was added to dissolve the obtained precipitate. The solution was further heated at 100 ℃ for 8 hours to remove unreacted reagents.
(3) Loading the same amount of the above solutions into centrifuge tubes, centrifuging with high speed centrifuge (12000rpm 10min 26 deg.C) to obtain red precipitate, removing supernatant, adding equal volume of ultrapure water for redissolution, centrifuging for 3 times, and collecting control pSC 4 -AuNPs @ Cu-MOFs stored at 4 ℃.
(4) Electrochemical measurement test: first, 20. Mu.L of 1nM PQ was added dropwise to the control pSC adhered thereto 4 And (3) treating the surface of a glassy carbon electrode of AuNPs @ Cu-MOFs for 40min to obtain a PQ treated glassy carbon electrode, and putting the PQ treated glassy carbon electrode into electrolyte for an Electrochemical Impedance Spectroscopy (EIS) test.
Wherein, three electrode system: the whole sensor consists of an electrochemical workstation of a three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, a working electrode is a glassy carbon electrode modified with a metal organic framework structure, and a liquid to be detected is used as an electrolyte. Electrolyte conditions: PBS buffer solution containing 5mM potassium ferricyanide at pH =7.4 was used as electrolyte for experimental detection.
After repeated experiments, the results show that: after the addition of PQ, no desired signal is generated. Description of pSC 4 AuNPs @ Cu-MOFs cannot recognize PQ by a host or detect PQ by an electrochemical method.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (6)
1. The application of an electrochemical biosensor based on a supermolecule host-guest recognition technology in detecting small molecular substances; the small molecular substance is selected from one of paraquat, acetamiprid, isoproturon or basic malachite green, and the electrochemical biosensor comprises: modified nanoparticles and a ZIF-8 metal organic framework;
the modified nano-particles are compounded with the ZIF-8 metal organic framework; the modified nano particle is 4-sulfonyl cup [4 ]]Aromatic hydrocarbon pSC 4 Coating the periphery of the metal nano particles;
the preparation method of the electrochemical biosensor is characterized by comprising the following steps:
step 1, mixing a zinc source, dimethyl imidazole and a solvent to obtain a ZIF-8 solution;
step 2, mixing the modified nanoparticle solution with the ZIF-8 solution, and centrifuging to obtain a precipitate, wherein the precipitate is an electrochemical biosensor based on a supramolecular host-guest recognition technology; wherein the modified nanoparticle solution is 4-sulfonyl cup [4 ]]Aromatic hydrocarbon pSC 4 And a metal nanoparticle;
wherein the feeding ratio of the modified nanoparticle solution to the ZIF-8 solution is (2-10): 44;
the detection of the application comprises:
s1, soaking a glassy carbon electrode in a pSC4-AuNPs @ ZIF-8 solution to enable the pSC4-AuNPs @ ZIF-8 to be attached to the surface of the glassy carbon electrode;
s2, dropwise adding PQ to the surface of the glassy carbon electrode attached with the pSC4-AuNPs @ ZIF-8, and treating for 10-50 min to obtain a PQ treated glassy carbon electrode;
and S3, putting the PQ-processed glassy carbon electrode into an electrolyte to measure the electrochemical impedance change of a three-electrode system.
2. The use of the electrochemical biosensor based on supramolecular guest-host recognition technology in the detection of small molecular substances as claimed in claim 1, wherein the metal nanoparticles are selected from one or more of nanogold, nanosilver, gold nanorods, gold nanoclusters, silver nanorods and silver-gold nanoclusters.
3. Electrochemical biosensor based on supramolecular host-guest recognition technology as claimed in claim 1 in detecting small moleculesUse in a sub-substance, characterized in that, in step 1, the zinc source is selected from Zn (OH) 2 Or Zn (NO) 3 ) 2 ·6H 2 O、ZnCl 2 And ZnSO 4 One or more of (a).
4. Use of the supramolecular host-guest recognition technology-based electrochemical biosensor in the detection of small molecule substances as claimed in claim 1, wherein the solvent is water.
5. The application of the electrochemical biosensor based on supramolecular host-guest recognition technology in detecting small molecular substances as claimed in claim 1, wherein in step 2, the preparation method of the modified nanoparticle solution comprises: deionized water and HAuCl 4 Solution, pSC 4 Mixing the solution to obtain a mixed solution, and then adding NaBH 4 And mixing the solution with the mixed solution to prepare the modified nano particle solution.
6. Use of the supramolecular host-guest recognition technology-based electrochemical biosensor in the detection of small molecule substances as claimed in claim 1, wherein step 2 is followed by a purification process comprising: and (3) re-dissolving the electrochemical biosensor based on the supermolecule host-guest recognition technology, centrifuging, and repeating for 1-3 times to obtain the electrochemical biosensor based on the supermolecule host-guest recognition technology.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011500136.0A CN112730561B (en) | 2020-12-17 | 2020-12-17 | Electrochemical biosensor based on supermolecule host-guest recognition technology and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011500136.0A CN112730561B (en) | 2020-12-17 | 2020-12-17 | Electrochemical biosensor based on supermolecule host-guest recognition technology and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112730561A CN112730561A (en) | 2021-04-30 |
| CN112730561B true CN112730561B (en) | 2022-10-04 |
Family
ID=75602913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011500136.0A Active CN112730561B (en) | 2020-12-17 | 2020-12-17 | Electrochemical biosensor based on supermolecule host-guest recognition technology and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112730561B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109342529B (en) * | 2018-09-19 | 2021-02-23 | 上海大学 | Non-enzymatic glucose sensor and preparation method thereof |
| CN109540991A (en) * | 2018-09-20 | 2019-03-29 | 上海大学 | Functional metal organic framework material, FKN sensor of its building and preparation method thereof |
-
2020
- 2020-12-17 CN CN202011500136.0A patent/CN112730561B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112730561A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Rapid recognition and determination of tryptophan by carbon nanotubes and molecularly imprinted polymer-modified glassy carbon electrode | |
| CN110018141B (en) | Ratiometric fluorescence analysis method for detecting mercury ions | |
| CN102426868B (en) | Water-soluble graphene-noble-metal nano-composite and preparation method and application thereof | |
| Tao et al. | Fabrication of an electrochemical sensor based on spiropyran for sensitive and selective detection of fluoride ion | |
| CN107727717B (en) | Preparation method and application of polychlorinated biphenyl photoelectrochemical aptamer sensor | |
| CN109580744B (en) | Modified silicon dioxide nano-pore membrane modified electrode and preparation method and application thereof | |
| CN104280435A (en) | Graphene-modified glassy carbon electrode and preparation method and application of graphene-modified glassy carbon electrode | |
| CN109100408B (en) | Method for detecting glutathione in human serum based on FePc/N, B-rGO modified electrode | |
| CN103175884A (en) | High-sensitivity glucose biosensor and preparation method thereof | |
| Taheri et al. | Sensitive and selective determination of Cu2+ at d-penicillamine functionalized nano-cellulose modified pencil graphite electrode | |
| CN113504283B (en) | Preparation method and application of composite material modified electrode for detecting gallic acid | |
| Sun et al. | Fabrication of glucose biosensor for whole blood based on Au/hyperbranched polyester nanoparticles multilayers by antibiofouling and self-assembly technique | |
| CN106442649B (en) | A method of 1,5- dewatered grape sugar alcohol is detected based on EIS structure electrochemical biosensor | |
| CN104833718A (en) | Preparation method and application of pH release-type immunosensor | |
| Hua et al. | A highly selective “turn-on” electroanalysis strategy with reduced copper metal–organic frameworks for sensing histamine and histidine | |
| KR101755230B1 (en) | Sensor for detecting multidrug resistance cancer cell and detecting method of multidrug resistance cancer cell using the same | |
| CN112630279B (en) | Gold nanoparticle-based plasma resonance enhanced electrochemical luminescence sensor for detecting dichlorophenolic acid and preparation method thereof | |
| CN112730561B (en) | Electrochemical biosensor based on supermolecule host-guest recognition technology and preparation method and application thereof | |
| Zhao et al. | A novel amperometric nitric oxide sensor based on imprinted microenvironments for controlling metal coordination | |
| CN107102052B (en) | Based on the uric acid electrochemical sensor containing active copper carbon dots and its application | |
| CN105806832B (en) | A kind of preparation method and application of the hydrogen peroxide sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry | |
| Ye et al. | Electrodeposition immobilized molybdenum disulfide quantum dots and their electrochemiluminescence application in the detection of melamine residues in milk powder | |
| CN111693593A (en) | Silicon dioxide uniform pore membrane for H in blood2Electrochemical luminescence detection method of S | |
| CN103994993A (en) | Photoelectric sensor based on functionalized triphenylamine dye TiO2 nano composite | |
| CN103512937A (en) | Modified electrode and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230109 Address after: North side of 22/F, Block B, Lianchuang Technology Building, No. 16, Jihui Road, Gulou District, Nanjing, Jiangsu, 210000 Patentee after: Nanjing Zhongweidian Environmental Protection Technology Co.,Ltd. Address before: 510275 No. 135 West Xingang Road, Guangdong, Guangzhou Patentee before: SUN YAT-SEN University |
|
| TR01 | Transfer of patent right |