CN110794015B - Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol - Google Patents
Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol Download PDFInfo
- Publication number
- CN110794015B CN110794015B CN201911181197.2A CN201911181197A CN110794015B CN 110794015 B CN110794015 B CN 110794015B CN 201911181197 A CN201911181197 A CN 201911181197A CN 110794015 B CN110794015 B CN 110794015B
- Authority
- CN
- China
- Prior art keywords
- graphene
- nonyl phenol
- sensor
- polypyrrole
- electrode
- 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a preparation method of a graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol. The invention discloses a novel molecularly imprinted electrochemical sensor for measuring nonyl phenol, which is constructed on the basis of a Graphene (GR)/polypyrrole (PPy) nano composite material by taking dopamine as a functional monomer. The results of electrochemical tests of Cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV) show that the GR/PPy modified molecularly imprinted sensor has good specific recognition capability and better selectivity and sensitivity for 4-NP. Response current (. DELTA.I) with nonyl phenol at 2.0X 10 ‑5 ～8.0×10 ‑10 molL ‑1 Has a good linear relationship with the negative logarithm (-lgC) of the concentration in the range of (1), and the detection limit of the imprinted sensor is 2.75X 10 ‑11 mol/L (S/N = 3). The electrochemical imprinting sensor realizes effective detection of nonyl phenol in water, and the recovery rate is 92-103%.
Description
Technical Field
The invention belongs to the technical field of electroanalytical chemistry and material synthesis, and particularly relates to a preparation method and application of a graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol.
Background
Nonylphenol (4-NP) is widely present in media used in manufacturing, e.g., as a lubricating oil additive, antioxidant, etc., while nonylphenol is also a degradation product of nonionic alkylphenol polyoxyethylene ether-based surfactants. The presence of nonylphenol has also been detected in food packaging films, plastics, toys and food in contact with food. Nonyl phenol has strong toxicitySeriously polluting the environment and the natural ecology. As endocrine disrupter, when the concentration in the environment reaches 10 -6 In time, it can interfere with the reproduction system of fish, reptiles and mammals, and bring serious harm to the living environment and physical and psychological health of people. Therefore, it is important to perform rapid, sensitive and highly selective detection of nonylphenol.
The detection method of the paranonyl phenol mainly comprises a solid phase microextraction-gas chromatography-mass spectrometry combined technology and a liquid chromatogram with a coulomb array. The gas chromatography-mass spectrometry (LC-MS) technology is better applied to trace analysis due to the characteristics of high sensitivity, good selectivity, high reliability and the like. However, these detection techniques require complex instrumentation and relatively time-consuming extraction procedures. In comparison, the electrochemical detection method has the advantages of low cost, simple operation, rapidness, high efficiency and the like. Nowadays, the method for detecting nonyl phenol by adopting an electrochemical sensing technology of an enzyme electrode and a non-enzyme electrode and the oxidation peak intensity of nonyl phenol is better applied, for example, a glassy carbon electrode, a platinum electrode, a gold electrode, a boron-doped diamond electrode and the like are adopted to analyze and detect nonyl phenol.
The electrochemical sensor based on molecular imprinting has higher sensitivity, selectivity and reproducibility because the molecular imprinting and the electrochemical sensor are effectively combined together. For example, ai et al use a molecular imprinting sensor based on modification of Au nanoparticles, multiwalled carbon nanotubes and graphene to realize high-sensitivity detection of nonyl phenol; huang et al on TiO 2 The molecular imprinting sensor modified by Au nano particles detects nonyl phenol, and the linear range of the molecular imprinting sensor is 4.80 multiplied by 10 −4 to 9.50×10 −7 mol L −1 (r = 0.998) and the detection limit was 3.20 × 10- 7 mol L −1 (ii) a Reduction of NH by electrochemical reduction by Chen et al 2 The functionalized Graphene Oxide (GO) is used for preparing the graphene modified nonylphenol molecular imprinting sensor, the linear range of the sensor is 0.01-1.0 mu g/L, and the detection limit of the sensor is 0.0035 mu g/L.
It can be seen that graphene has also been widely used in electrochemical sensors due to its large surface area, good electrical conductivity and electrocatalytic properties, while conducting polymers, in particular polypyrrole, have been widely used in applications such as catalyst supports for fuel cells, drug delivery, optics, batteries, supercapacitors and sensors. Research shows that the composite material composed of polypyrrole and graphene can be directly used for an electrode or modifying the electrode due to more active sites and larger surface area so as to improve the detection capability of the electrochemical sensor on target molecules.
Disclosure of Invention
The invention aims to provide a preparation method and application of a graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol, the imprinted sensor has low detection limit and high selectivity, can be used for high-sensitivity detection of nonyl phenol in an actual sample, and provides a new effective way for preparation and practical application of a nonyl phenol electrochemical sensor.
The technical scheme of the invention is as follows:
the purpose of the invention is realized as follows: the graphene/polypyrrole nano composite material is prepared by an in-situ oxidation polymerization method, and then the nonyl phenol imprinted sensor is prepared by electrochemical polymerization by taking dopamine as a functional monomer and nonyl phenol as an imprinted molecule. The method comprises the following specific steps:
(1) Preparing a graphene/polypyrrole nano composite material: putting 10 mg Graphene Oxide (GO) into 15 mL deionized water, and performing ultrasonic treatment on 1 h to uniformly mix GO dispersion liquid; 1 mL pyrrole monomer (Py) is put into an ice-water bath, and 2 h is stirred strongly; putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12 h; and centrifuging the obtained substance, sequentially using deionized water and ethanol, centrifuging and washing the substance for three times, and finally drying the substance in a freeze dryer to obtain the graphene/polypyrrole nano composite material (GR/PPy).
(2) Preparing a graphene/polypyrrole nanocomposite modified molecularly imprinted sensor: 10 mg of GR/PPy composite material is taken to form uniform dispersion liquid in 10 mL distilled water, and the graphene/polypyrrole modified carbon electrode (GR/PPy/CE) is obtained by circularly scanning ten circles (cyclic potential: 1.3V to 1V, scanning speed: 0.025V/s) through cyclic voltammetry. The GR/PPy/CE electrode was used as a working electrode, and the electrode was placed in 25mL of ethanol, and 0.05g of nonylphenol and 5.0mmol of dopamine were added and mixed uniformly. And (3) electrodepositing 8 circles by using cyclic voltammetry (cyclic potential: 0-0.8V, scanning rate: 0.025V/s) to obtain the GR/PPy modified nonylphenol imprinted sensor (MIP/GR/PPy/CE). And placing the obtained imprinted sensor in an eluent of methanol and acetic acid to elute the template molecules, wherein the ratio of the methanol to the acetic acid in the eluent is 7:3, and the elution time is 8min.
The molecularly imprinted sensor prepared by the preparation method of the graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol is used for detecting nonyl phenol.
The specific detection method comprises the following steps:
(1) Placing the eluted nonylphenol imprinted sensor in a nonylphenol solution for incubation for 16 minutes, and then performing DPV (differential pressure vacuum) test in a PBS (phosphate buffer solution);
(2) And (3) electrochemical detection: selecting a three-electrode system with a calomel electrode as a reference electrode, a 5mm multiplied by 5mm platinum wire electrode as an auxiliary electrode and a modified carbon electrode as a working electrode, weighing 0.4938g of potassium ferricyanide, and dissolving the potassium ferricyanide in 30mL of water to prepare 5.0 multiplied by 10 -3 mol/L[Fe(CN) 6 ] 3-/4- The PBS solution (2) is subjected to cyclic voltammetry and differential pulse voltammetry detection, wherein the cyclic potential is set to-0.4 to 0.8V, the scanning speed is set to 0.05V/s, the DPV pulse potential is set to 0 to 0.4V, and the scanning speed is 0.05V/s in CV test.
The invention has the beneficial effects that:
1. the graphene/polypyrrole nanocomposite is prepared by an in-situ intercalation polymerization method, dopamine is used as a functional monomer, nonyl phenol is used as an imprinting molecule, a nonyl phenol imprinting sensor modified by the graphene/polypyrrole nanocomposite is prepared by an electrochemical polymerization method, and a new way is provided for effective detection of nonyl phenol.
2. According to the graphene/polypyrrole nano composite material prepared by the invention, due to the in-situ intercalation effect of polypyrrole, the agglomeration phenomenon of graphene oxide is effectively avoided, and the stability of the material is improved. Meanwhile, the graphene oxide is reduced into graphene through hydrothermal treatment, so that the conductivity of the material is improved, and the internal resistance is reduced. All the methods provide guarantee for the stable and effective detection of the nonyl phenol by the imprinting sensor.
3. According to the invention, the graphene/polypyrrole nano composite material is modified on the carbon electrode by an electrodeposition method, and the molecularly imprinted membrane is further prepared on the surface of the graphene/polypyrrole nano composite material by electrodeposition, so that the modified material is stable and not easy to fall off, and the thickness of the modified material is uniform and controllable.
4. The molecular imprinting membrane prepared by taking dopamine as a functional monomer fully ensures the sensitivity and selectivity of the prepared nonylphenol imprinting sensor due to the film forming property and biocompatibility of the dopamine, and further lays a foundation for the practical application of the prepared nonylphenol imprinting sensor.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of GO (a), GR/PPy (b), MIP/GR/PPy/CE before (c) and after (d) elution of the present invention.
FIG. 2 CV (A) and DPV (B) plots of modified electrodes of the invention: CE (a), GO/CE (b), GR/PPy/CE (c), MIP/GR/PPy/CE (d), and eluted MIP/GR/PPy/CE (e).
FIG. 3 is a graph showing the relationship between the DPV response value of the present invention and the ratios of eluents (A), elution times (B) and incubation times (C).
FIG. 4 is a graph (B) showing the negative logarithm (-lgC) of the response (A) and response current (Δ I) to 4-NP concentration of DPV of the present invention versus 4-NP concentration at different concentrations.
Detailed Description
The invention is further described below in conjunction with the appended drawings and detailed description so that those skilled in the art may better understand the invention, but the invention is not limited thereto.
Nonyl phenol (4-NP) is endocrine interferon which can affect development and has strong toxicity, so that the detection of nonyl phenol is important. The invention discloses a novel molecularly imprinted electrochemical sensor for measuring nonyl phenol, which is constructed on the basis of a Graphene (GR)/polypyrrole (PPy) nano composite material by taking dopamine as a functional monomer. Circulation voltageThe electrochemical test results of ampere (CV) and Differential Pulse Voltammetry (DPV) show that the GR/PPy modified molecularly imprinted sensor has good specific recognition capability and better selectivity and sensitivity for 4-NP. Response current (. DELTA.I) with nonyl phenol at 2.0X 10 -5 ~8.0×10 -10 molL -1 Has a good linear relationship with the negative logarithm (-lgC) of the concentration of the range of (A), and the detection limit of the imprinted sensor is 2.75X 10 - 11 mol/L (S/N = 3). The electrochemical imprinting sensor realizes effective detection of nonyl phenol in water, and the recovery rate is 92-103%. The highest value of 4-NP allowed by combining the environment recommended by the country is 1 mug/L, so that the method provides a new effective way for the preparation and the practical application of the nonyl phenol electrochemical sensor.
Examples
1. Putting the prepared 10 mg Graphene Oxide (GO) into 15 mL deionized water, and performing ultrasonic treatment on 1 h to uniformly mix GO dispersion liquid; 1 mL pyrrole monomer (Py) is put in an ice-water bath condition, and 2 h is stirred strongly; putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12 h; centrifuging the obtained substance, sequentially using deionized water and ethanol to centrifugally wash the substance for three times, and finally drying the substance in a freeze dryer to obtain the graphene/polypyrrole nano composite material (GR/PPy). 10 mg of GR/PPy composite material is taken to form uniform dispersion liquid in 10 mL distilled water, and the graphene/polypyrrole modified carbon electrode (GR/PPy/CE) is obtained by circularly scanning ten circles (cyclic potential: 1.3V to 1V, scanning speed: 0.025V/s) through cyclic voltammetry. The GR/PPy/CE electrode was used as a working electrode, and the electrode was placed in 25mL of ethanol, and 0.05g of nonylphenol and 5.0mmol of dopamine were added and mixed uniformly. And (3) electrodepositing 8 circles by using cyclic voltammetry (cyclic potential: 0-0.8V, scanning rate: 0.025V/s) to obtain the GR/PPy modified nonylphenol imprinted sensor (MIP/GR/PPy/CE). FIG. 1 is a Scanning Electron Micrograph (SEM) of GO (a), GR/PPy (b), MIP/GR/PPy/CE before (c) and after (d) elution. It can be observed in fig. 1B that the intercalated graphene is loaded with polypyrrole nanoparticles, with particle diameters around 13 nm. Due to the intercalation of polypyrrole, graphene sheets are further dispersed, the defect that graphene is easy to agglomerate is overcome, the specific surface area of the composite material is increased, and the good electrochemical performance of the composite material modified electrode is guaranteed. FIG. 1C is a surface topography of an imprinted membrane formed by polymerizing dopamine containing nonylphenol imprinted molecules on the GR/PPy modified electrode surface by an electrochemical polymerization method, and the membrane is relatively intact. Fig. 1D shows the surface morphology of the molecularly imprinted membrane after elution, and texture structure formed on the surface of the membrane due to elution can be observed.
2. Electrochemical performance tests were performed on the modified electrodes using cyclic voltammetry in a PBS solution of potassium ferricyanide, and the results are shown in figure 2. In FIG. 2A, curve a is the cyclic voltammogram of CE, and a distinct redox peak can be observed; when GO is modified on the surface of CE, the oxidation-reduction peak is enhanced, because the oxidation-reduction of potassium ferricyanide is enhanced due to the electrical conductivity of GO, as shown in a curve b; for GR/PPy/CE, the specific surface area of GR and the intercalation of PPy increase the conductive capability of GR, promote the electron transfer, so that the oxidation-reduction peak is further increased, as shown in graph c; when nonylphenol was imprinted on the electrode surface using dopamine as functional monomer, the peak current was significantly reduced due to the inhibition of electron transfer by the surface nonylphenol molecules, as shown in graph d; when nonylphenol was eluted, the peak current value of the resultant blotting electrode was significantly increased again (fig. e), as a result of factors hindering electron transfer after elution being eliminated. The response of the imprinting molecules to electrochemistry is proved by comparing the circulation curves before and after elution.
FIG. 2B is a DPV contrast plot (potentials set at-0.2 to 0.5V) for CE, GO/CE, GR/PPy/CE, MIP/GR/PPy/CE, and MIP/GR/PPy/CE after elution in PBS. Due to the conductivity of GR and the intercalation of conductive polymer PPy, the current response of GR/PPy/CE is obviously increased. When nonylphenol is imprinted on GR/PPy/CE, the response current is significantly reduced due to the blocking effect of the nonylphenol molecules on electron transfer, as shown by curve d in FIG. 2B; when nonylphenol was eluted, the response current value of the blotting electrode was again significantly increased (FIGS. 2B-e), consistent with the responsiveness of CV.
3. Will getThe obtained imprinted sensor is placed in an eluent of methanol and acetic acid to elute the template molecule, and the elution effect is achieved by controlling the ratio of the methanol to the acetic acid in the eluent and the elution time. Eluting the engram molecules by using eluents with different proportions, and then eluting the engram molecules at 5.0 multiplied by 10 -3 mol/L[Fe(CN) 6 ] 3-/4- The PBS solution of (a) was subjected to DPV test. As shown in the following figure, the elution effect was the best under the condition that the volume ratio of methanol to acetic acid was 7:3 at the same elution time (FIG. 3A). DPV tests were also performed on MIP/GR/PPy/CE in PBS at different elution times, which indicated an optimal elution time of 8min (FIG. 3B). For MIP/GR/PPy/CE after elution, 2.0X 10 -5 The incubation time was optimized in mol/L nonylphenol solution, and the DPV response current was substantially stabilized at around 0.03mA after incubation for 16 minutes, so that it was determined that the optimal incubation time was 16 minutes (fig. 3C).
4. The DPV method with high sensitivity is adopted to test the electrochemical corresponding performance of the imprinted sensor on nonyl phenol with different concentrations (figure 4A). The eluted MIP/GR/PPy/CE was placed at a concentration of 2X 10, respectively -5 ，8×10 -6 ，2×10 -6 ，8×10 -7 ，2×10 -7 ，8×10 -8 ，2×10 -8 ，8×10 -9 ，2×10 -9 ，8×10 -10 Soaking in nonyl phenol solution in mol/L, and after 16 minutes, performing DPV test in PBS solution. The results show that the response current value of the blank test is the largest, and the response current value becomes smaller and the response current DeltaI gradually increases as the concentration of the nonyl phenol increases. This is because specific binding occurs between nonyl phenol and the binding site on the electrode surface of the imprinted sensor after elution, so that the diffusion flux of electrons is reduced, and the current value shows a regular gradient decrease as the concentration gradient increases. As shown in FIG. 4B, the response current (. DELTA.I) of the imprinted sensor was 2X 10 with nonylphenol -5 ~8.0×10 -10 The negative logarithm of concentration (-lgC) in the mol/L range is in good linear relation, the linear equation is DeltaI (mA) =0.018lgC (mol/L) +0.19, the correlation coefficient R =0.996, and the detection limit of the imprinted sensor is 2.75X 10-11mol/L (S/N = 3).
5、Selectivity and reproducibility experiments: selecting substance with similar structure of octyl phenol, bisphenol A and nonyl phenol as interference substance, and preparing the concentration of the interference substance to be 2 multiplied by 10 -5 And (3) putting the imprinting sensor into two solutions of octylphenol and bisphenol A at mol/L respectively, incubating for 16 minutes, taking out, and testing DPV in a PBS solution by using a three-electrode system. The result shows that the response current delta I of the electrode to octylphenol and bisphenol A is 0.034mA and 0.011mA respectively, the response current of the imprinted sensor to nonylphenol is the maximum, and the good selectivity of the sensor to nonylphenol is proved. When the same imprinted sensor is used for repeated elution and three detections are carried out on nonylphenol solution with the concentration of 2X 10-5 mol/L, the response current Delta I is reduced by only 10.6 percent compared with the primary detection value, which indicates that the imprinted sensor has good reproducibility.
6. Practical experiments of GR/PPy modified nonylphenol imprinted sensor: tap water, snow water and rural river water in a laboratory are selected as test samples. The method comprises the steps of taking three samples, filtering the samples by using a microporous filtering membrane respectively, adding nonylphenol with corresponding concentration respectively, placing a nonylphenol imprinted sensor in the samples, incubating for 16 minutes, testing a response current value by using a three-electrode system in a prepared PBS (phosphate buffer solution) solution by using a differential pulse method, and substituting a value of delta I into a linear equation to obtain the detection concentration, wherein as shown in Table 1, the recovery rate of the nonylphenol in the three water samples by using the imprinted sensor prepared by the method is 92% -103%, so that the obtained GR/PPy modified nonylphenol imprinted sensor can be applied to detection of the nonylphenol in actual water samples, and has practical value.
Claims (3)
1. A preparation method of a graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol is characterized by comprising the following steps:
the method comprises the following specific steps:
(1) Preparing a graphene/polypyrrole nano composite material: putting 10 mg graphene oxide into 15 mL deionized water, and performing ultrasonic treatment on 1 h to uniformly mix GO dispersion liquid; 1 mL pyrrole monomer is put under the condition of ice-water bath, and 2 h is stirred strongly; putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 12 h; centrifuging the obtained substance, sequentially using deionized water and ethanol, then centrifuging and washing the substance for three times, and finally drying the substance in a freeze dryer to obtain the graphene/polypyrrole nano composite material;
(2) Preparing a graphene/polypyrrole nanocomposite modified molecularly imprinted sensor: taking 10 mg GR/PPy composite material to form uniform dispersion liquid in 10 mL distilled water, obtaining a graphene/polypyrrole modified carbon electrode by cyclic sweep for ten circles through cyclic voltammetry, taking the GR/PPy/CE as a working electrode, putting the working electrode into 25mL of ethanol, adding 0.05g of nonylphenol and 5.0mmol of dopamine to mix uniformly, carrying out electrodeposition for 8 circles through cyclic voltammetry to obtain a GR/PPy modified nonylphenol imprinted sensor, putting the obtained imprinted sensor into eluent of methanol and acetic acid to elute a template molecule, wherein the ratio of methanol to acetic acid in the eluent is 7:3, and the elution time is 8min.
2. The molecularly imprinted sensor prepared by the preparation method of the graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol according to claim 1 is used for detecting nonyl phenol.
3. The method for detecting nonyl phenol of claim 2, wherein the molecularly imprinted sensor prepared by the method for preparing the graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol is used for detecting nonyl phenol, and is characterized in that: the specific detection method comprises the following steps:
(1) Placing the eluted nonylphenol imprinted sensor in a nonylphenol solution for incubation for 16 minutes, and then performing DPV (differential pressure vacuum) test in a PBS (phosphate buffer solution);
(2) Detection by an electrochemical method: selecting a three-electrode system with a calomel electrode as a reference electrode, a platinum wire electrode as an auxiliary electrode and a modified carbon electrode as a working electrode, weighing 0.4938g of potassium ferricyanide, and dissolving the potassium ferricyanide in 30mL of water to prepare 5.0 multiplied by 10 -3 mol/L[Fe(CN) 6 ] 3-/4- The PBS solution of (1) is subjected to cyclic voltammetry and differential pulse voltammetry detection, wherein the cyclic potential is set to-0.4-0.8V, the scanning speed is set to 0.05V/s, the DPV pulse potential is set to 0-0.4V, and the scanning speed is 0.05V/s during CV test.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911181197.2A CN110794015B (en) | 2019-11-27 | 2019-11-27 | Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911181197.2A CN110794015B (en) | 2019-11-27 | 2019-11-27 | Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110794015A CN110794015A (en) | 2020-02-14 |
| CN110794015B true CN110794015B (en) | 2023-04-07 |
Family
ID=69446389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911181197.2A Active CN110794015B (en) | 2019-11-27 | 2019-11-27 | Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110794015B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111198119A (en) * | 2020-02-25 | 2020-05-26 | 南京海关工业产品检测中心 | Method for detecting octylphenol in textile based on molecular imprinting technology |
| CN111198120A (en) * | 2020-02-25 | 2020-05-26 | 南京海关工业产品检测中心 | Method for detecting nonyl phenol in textile based on molecular imprinting technology |
| CN111551597A (en) * | 2020-05-29 | 2020-08-18 | 西安工程大学 | Polypyrrole composite electromagnetic wave absorbing material, preparation method and application |
| CN112964769B (en) * | 2021-03-31 | 2023-08-15 | 常州市新鸿医药化工技术有限公司 | Method for rapidly detecting folic acid content |
| CN114870896A (en) * | 2022-04-24 | 2022-08-09 | 陕西科技大学 | 2D/2D photocatalysis-photothermal composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109254053A (en) * | 2018-11-05 | 2019-01-22 | 济南大学 | A kind of preparation method and application of environmental estrogens electro-chemical analyzing sensor |
| CN109781815A (en) * | 2019-01-29 | 2019-05-21 | 天津科技大学 | A kind of preparation method of olaquindox molecular engram film electrochemical sensor |
-
2019
- 2019-11-27 CN CN201911181197.2A patent/CN110794015B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109254053A (en) * | 2018-11-05 | 2019-01-22 | 济南大学 | A kind of preparation method and application of environmental estrogens electro-chemical analyzing sensor |
| CN109781815A (en) * | 2019-01-29 | 2019-05-21 | 天津科技大学 | A kind of preparation method of olaquindox molecular engram film electrochemical sensor |
Non-Patent Citations (2)
| Title |
|---|
| Facile Fabrication of Three-Dimensional Lightweight RGO/PPy Nanotube/Fe3O4 Aerogel with Excellent Electromagnetic Wave Absorption Properties;Chunmei Zhang等;《ACS Omega》;20180529;第3卷;第5735-5743页 * |
| 磁性石墨烯修饰辛基酚印迹传感器制备及应用研究;龙芳等;《分析化学》;20160615(第06期);第908-914页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110794015A (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110794015B (en) | Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol | |
| Yuan et al. | Electrochemical sensor based on molecularly imprinted membranes at platinum nanoparticles-modified electrode for determination of 17β-estradiol | |
| Shahrokhian et al. | Application of thionine-nafion supported on multi-walled carbon nanotube for preparation of a modified electrode in simultaneous voltammetric detection of dopamine and ascorbic acid | |
| Qian et al. | Research progress of electrochemical detection of heavy metal ions | |
| Singh et al. | One step electrochemical synthesis of gold-nanoparticles–polypyrrole composite for application in catechin electrochemical biosensor | |
| Wei et al. | Selective detection toward Hg (II) and Pb (II) using polypyrrole/carbonaceous nanospheres modified screen-printed electrode | |
| Huang et al. | Synthesis of a novel electrode material containing phytic acid-polyaniline nanofibers for simultaneous determination of cadmium and lead ions | |
| Gu et al. | Double recognition of dopamine based on a boronic acid functionalized poly (aniline-co-anthranilic acid)–molecularly imprinted polymer composite | |
| Dang et al. | A novel electrochemical sensor for the selective determination of hydroquinone and catechol using synergic effect of electropolymerized nicotinic acid film and Cd-doped ZnWO4 nanoneedle | |
| Yu et al. | Electrochemical Behavior and Determination of L‐Tyrosine at Single‐walled Carbon Nanotubes Modified Glassy Carbon Electrode | |
| Li et al. | Electrocatalytic reduction of trace nitrobenzene using a graphene-oxide@ polymerized-manganese-porphyrin composite | |
| Li et al. | Electrochemical detection of ractopamine based on a molecularly imprinted poly-o-phenylenediamine/gold nanoparticle–ionic liquid–graphene film modified glass carbon electrode | |
| Nie et al. | Simultaneous determination of folic acid and uric acid under coexistence of L-ascorbic acid using a modified electrode based on poly (3, 4-ethylenedioxythiophene) and functionalized single-walled carbon nanotubes composite | |
| Zhang et al. | A molecularly imprinted electrochemical sensor based on cationic intercalated two-dimensional titanium carbide nanosheets for sensitive and selective detection of triclosan in food samples | |
| Liu et al. | Novel cysteic acid/reduced graphene oxide composite film modified electrode for the selective detection of trace silver ions in natural waters | |
| Azodi-Deilami et al. | Determination of meloxicam in plasma samples using a highly selective and sensitive voltammetric sensor based on carbon paste electrodes modified by molecularly imprinted polymer nanoparticle–multiwall carbon nanotubes | |
| Mardani et al. | Preparation of molecularly imprinted magnetic graphene oxide-gold nanocomposite and its application to the design of electrochemical sensor for determination of epinephrine | |
| Lu et al. | Determination of Uric Acid and Norepinephrine by Chitosan‐Multiwall Carbon Nanotube Modified Electrode | |
| Dong et al. | Amperometric Biosensor for Detection of Phenolic Compounds Based on Tyrosinase, N‐Acetyl‐L‐cysteine‐capped Gold Nanoparticles and Chitosan Nanocomposite | |
| Upadhyay et al. | A biosensor for hydrogen peroxide based on single walled carbon nanotube and metal oxide modified indium tin oxide electrode | |
| Liang et al. | Potentiometric sensor based on an ion-imprinted polymer for determination of copper | |
| Yang et al. | Direct determination of uric acid in human serum samples using polypyrrole nanoelectrode ensembles | |
| Wu et al. | Construction of a selective non-enzymatic electrochemical sensor based on hollow nickel nanospheres/carbon dots–chitosan and molecularly imprinted polymer film for the detection of glucose | |
| CN211122646U (en) | L-glutamic acid detection sensor based on molecularly imprinted polymeric membrane modified electrode | |
| CN112858428B (en) | Electrochemical sensor for detecting bisphenol A and bisphenol S based on covalent organic framework modified graphite core electrode |
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 |