CN111855768A - Preparation method of phenol molecular imprinting sensor - Google Patents
Preparation method of phenol molecular imprinting sensor Download PDFInfo
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- CN111855768A CN111855768A CN202010402282.3A CN202010402282A CN111855768A CN 111855768 A CN111855768 A CN 111855768A CN 202010402282 A CN202010402282 A CN 202010402282A CN 111855768 A CN111855768 A CN 111855768A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 126
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- 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
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- 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
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Abstract
The invention discloses a preparation method of a phenol molecular imprinting sensor, which comprises the following steps: preparing a phenol molecularly imprinted polymer; pretreating a gold electrode; and (3) preparing the molecularly imprinted electrochemical sensor. Phenol is taken as a target molecule, acrylamide is taken as a functional monomer, methacrylamide is taken as a cross-linking agent, azodiisobutyronitrile is taken as an inducing agent, and a mass polymerization reaction is adopted to prepare the phenol molecularly imprinted polymer. And then, by means of a gold electrode, the adsorption process of the polymer on the gold electrode is enhanced by utilizing the sensitization of the chitosan, and the phenol molecular imprinting electrochemical sensor is prepared, is used for measuring the phenol content, has obvious effect and has the detection limit of 3.55 multiplied by 10‑9mg/L。
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a preparation method of a phenol molecular imprinting sensor.
Background
Phenol is a highly toxic substance, is used as a basic raw material in organic chemical industry, and can pollute environmental water bodies through various ways. When the phenol content in the water is more than 5mg/L, the fish can be poisoned and killed; the migration and propagation of the fishes can be influenced when the concentration of the phenol in the water is low. Phenol is a protoplasmic poison (i.e., acts directly on protoplasmic protein) and can solidify or denature protein, and acute poisoning symptoms can occur when a human body intakes a certain amount of phenol. Therefore, the method has important significance for detecting the content of phenol in the environment.
The methods commonly used for measuring phenol mainly include fluorescence analysis, sensor method, high performance liquid chromatography, spectrophotometry and the like. Detecting phenol in liquid phase by fluorescence analysis and spectrophotometry, wherein the detection limit of phenol in the fluorescence spectrophotometry is 2 x 10-3mg/L; steaming foodThe detection limit of the direct spectrophotometry after distillation is only 0.1 mg/L; the instrument used by the high performance liquid chromatography is high in price, and the phenol detection limit is only 8 multiplied by 10-5mg/L。
The molecular imprinting electrochemical sensor is a sensor prepared by combining a molecular imprinting technology with an electrochemical detection means, and has the advantages of low detection limit, high sensitivity, high selectivity and the like. The molecular imprinting electrochemical sensor combines the advantages that molecular imprinting has recognition selectivity similar to that of natural antibodies, avoids the defects of the traditional sensor, and greatly increases the selectivity and sensitivity of the traditional sensor. Through continuous development, the technology is more and more concerned by academia and industry. In the polymerization process of the molecularly imprinted polymer, a mass polymerization method is adopted to enable template molecule phenol to react with functional monomer propylene to generate the polymer. Bulk polymerization is a polymerization reaction initiated by the monomer itself polymerizing under the action of an initiator without the addition of a solvent or other dispersant. The prepared product is pure and has good electrical property. The molecularly imprinted polymer has specific recognition capability on target molecules, can be used as a recognition element of a sensor to construct a molecularly imprinted sensor according to the characteristic, obtains electric signals capable of being detected and recognized through magnetic, optical, electric, thermal and other conversion ways after the molecularly imprinted polymer is enriched and recognizes target compounds, and can obtain related information of the target molecules through the analyzable electric signals. Molecularly imprinted electrochemical sensors began to detect vitamins by Tabushi in 1987 for the first time using molecularly imprinted polymers as sensitive materials, and since this time, people have gained wide interest in molecularly imprinted electrochemical sensors. The Shegano root and the like adopt an electric polymerization method to prepare the polypyrole film by taking salicylic acid as a target molecule, and the imprinted electrode can enhance the electric oxidation process of the salicylic acid. At present, the preparation of the molecular imprinting electrochemical sensor basically adopts an electropolymerization method, and the research for preparing the electrochemical sensor based on the molecular imprinting and self-assembly technology is few, so the preparation method of the phenol molecular imprinting sensor is required in the market.
Disclosure of Invention
The invention provides a preparation method of a phenol molecular imprinting sensor, which overcomes the defects of the preparation of a molecular imprinting electrochemical sensor by adopting an electropolymerization method in the background technology.
The technical scheme adopted by the invention for solving the technical problem is as follows: the preparation method of the phenol molecular imprinting sensor comprises the following steps:
step 1, preparing a phenol molecularly imprinted polymer;
adding 0.11-0.12 g of phenol and 1.95-2.05 g of acrylamide into 50ml of absolute ethanol, and uniformly mixing the absolute ethanol, the phenol and the acrylamide to prepare a mixed solution; adding 0.45-0.55 g of azobisisobutyronitrile and 0.95-1.05 g of methylene acrylamide into 50ml of absolute ethanol, adding the mixed solution, and uniformly mixing to prepare the phenol molecularly imprinted polymer;
step 2, pretreating a gold electrode;
spreading paste material prepared by mixing aluminum oxide powder and distilled water on the chamois surface, grinding the gold electrode on the chamois surface, and cleaning the surface of the gold electrode with distilled water; placing the treated gold electrode in H with the concentration of 97-99%2SO4And hydrogen peroxide according to the weight ratio of (6-8): 3Volume ofCleaning in the mixed solution mixed in proportion; placing the gold electrode in absolute ethyl alcohol for cleaning; placing the gold electrode in purified water for cleaning;
31, preparing 0.095-0.105 g/L chitosan solution, and placing the gold electrode in the step 2 into the solution to enable the chitosan to be gathered on the surface of the gold electrode; taking out the gold electrode, using N2Drying;
step 32, placing the dried gold electrode in a phenol molecular imprinting polymer for soaking so that the template molecular phenol is indirectly gathered on the gold electrode; taking out the gold electrode, using N2Drying by blowing, and drying the surface of the gold electrode to obtain a polymer modified electrode;
and 33, placing the modified electrode in 0.095-0.105 mol/LNaOH solution for elution, neutralizing sodium hydroxide and phenol, removing template molecule phenol, and leaving specific recognition holes of phenol molecules on an imprinting film on the surface of the gold electrode to obtain the phenol molecular imprinting electrochemical sensor.
In one embodiment: the step 1 comprises the following steps:
step 11, adding 0.11-0.12 g of phenol and 1.95-2.05 g of acrylamide into 50ml of absolute ethanol, and mixing the absolute ethanol, the phenol and the acrylamide; performing ultrasonic treatment for 25-35 minutes by using an ultrasonic cleaning machine, and standing for 25-35 minutes to uniformly mix to prepare a mixed solution;
In one embodiment: the step 2 comprises the following steps:
step 21, spreading a pasty material formed by mixing alumina powder and distilled water on the surface of the chamois, and grinding a gold electrode on the surface of the chamois; washing the surface of the gold electrode with distilled water;
step 22, placing the treated gold electrode in H with the concentration of 97-99%2SO4And hydrogen peroxide according to the weight ratio of (6-8): 3, cleaning the mixture in the mixed solution in a volume ratio for 5-7 minutes by adopting ultrasonic waves;
step 23, placing the gold electrode in absolute ethyl alcohol and cleaning for 5-7 minutes by adopting ultrasonic waves;
and 24, placing the gold electrode in purified water and cleaning for 5-7 minutes by adopting ultrasonic waves.
In one embodiment: this step 21 includes:
keeping the chamois smooth, and sprinkling a pasty material formed by mixing 0.8-1.2 mu m of aluminum oxide powder and distilled water on the chamois surface; the gold electrode is vertical to the chamois, the surface of the gold electrode needing to be polished is repeatedly polished on the chamois, and the mirror surface is washed by distilled water after polishing;
spreading a paste material prepared by mixing 0.25-0.35 μm aluminum oxide powder and distilled water on the surface of the chamois leather; the gold electrode is vertical to the chamois, the surface of the gold electrode needing to be polished is repeatedly polished on the chamois, and the mirror surface is washed by distilled water after polishing.
In one embodiment: the step 2 further comprises: and step 25, taking equal volumes of potassium chloride, potassium ferricyanide and potassium ferrocyanide, uniformly mixing the equal volumes of potassium chloride, potassium ferricyanide and potassium ferrocyanide to serve as a base solution, placing the gold electrode in the base solution for cyclic voltammetry, and when the peak current is stably maintained at a high level, indicating that the gold electrode has a good treatment effect.
In one embodiment: in the step 31, the gold electrode in the step 2 is placed in the solution for 7-9 hours;
in the step 32, the blow-dried gold electrode is placed in a phenol molecular imprinting polymer to be soaked for 7-9 hours;
in the step 33, the modified electrode is put into 0.095-0.105 mol/LNaOH solution for elution for 18-22 minutes.
Compared with the background technology, the technical scheme has the following advantages:
phenol is taken as a target molecule, acrylamide is taken as a functional monomer, methacrylamide is taken as a cross-linking agent, azodiisobutyronitrile is taken as an inducing agent, and a mass polymerization reaction is adopted to prepare the phenol molecularly imprinted polymer. And then, by means of a gold electrode, the adsorption process of the polymer on the gold electrode is enhanced by utilizing the sensitization of the chitosan, and the phenol molecular imprinting electrochemical sensor is prepared, is used for measuring the phenol content, has obvious effect and has the detection limit of 3.55 multiplied by 10-9mg/L。
The elution is limited within 18-22 min, so that the number of holes can be increased, the electric signal can be enhanced, and the phenomenon that the blotting sites are blocked and the electric signal is reduced due to slight swelling of the blotting membrane can be avoided.
Drawings
The invention is further described with reference to the following figures and detailed description.
FIG. 1 is a schematic diagram of the fabrication of a molecularly imprinted electrochemical sensor of a specific embodiment.
FIG. 2 is a differential pulse diagram of a bare electrode and a imprinted electrode of an embodiment.
FIG. 3 is a graph of differential pulses for different concentrations of phenol according to an embodiment.
FIG. 4 is a calibration curve of phenol response current for an embodiment.
Detailed Description
The preparation method of the phenol molecular imprinting sensor comprises the following steps:
step 1, preparing a phenol Molecularly Imprinted Polymer (MIPS);
50mL of absolute ethyl alcohol is measured in a clean beaker, 0.116g of phenol and 2g of acrylamide are weighed by an electronic balance and placed in the beaker, the beaker is placed in an ultrasonic cleaning machine to carry out ultrasonic treatment for 30min, and after the phenol and the acrylamide are completely and uniformly mixed, the beaker is taken out and is kept still for 30 min. The ultrasonic cleaning machine can be an ultrasonic cleaning machine with adjustable power (KQ5200DE, ultrasonic instruments ltd., Kunshan).
0.5g of azobisisobutyronitrile and 1g of methylene acrylamide are weighed by an electronic balance and placed in a beaker after standing, and the beaker is placed in an ultrasonic cleaning machine to be mixed for 30min and then taken out. The prepared mixed solution is sealed by a preservative film in a 500ml conical flask and then placed in a speed-regulating multipurpose oscillator, the temperature is set to be 25 ℃, the oscillation speed is medium, and the oscillation time is 8 hours. Through the operation, the mixed solution is fully reacted to prepare the milky white phenol Molecularly Imprinted Polymer (MIPS). The oscillator can be selected from speed-regulating multipurpose oscillator (HY-4 Jiangsu JintanCity Ronghua apparatus factory).
Meanwhile, Non-imprinted polymers (NIPs) without adding template molecule phenol are prepared, and the preparation method is different from the MIPS preparation in that: phenol is not added, the rest steps are the same as the preparation of MIPS, and the preparation of the non-imprinted polymer is used for the subsequent preparation of the non-imprinted electrochemical sensor.
Step 2, pretreating a gold electrode;
step 21, keeping the chamois smooth, and scattering a pasty material formed by mixing 1-micron aluminum oxide powder and distilled water on the chamois surface; the gold electrode is vertical to the chamois, the surface of the electrode to be polished is repeatedly ground on the chamois by winding the splayed pattern with proper force, and the mirror surface is washed by distilled water after polishing;
spreading a paste material prepared by mixing 0.3 μm alumina powder and distilled water on the surface of the chamois leather; the gold electrode perpendicular to chamois leather lets the face that the electrode needs to polish grind around the splayed and grinds on it repeatedly, and the dynamics is suitable can, polishes the back and washes the mirror surface with distilled water.
When the treatment effect is tested, a drop of distilled water can be dropped on the surface of the gold electrode, and if only one drop of distilled water is dropped in the middle mirror surface instead of covering the whole electrode plane, the treatment effect is better.
Step 22, placing the treated gold electrode in H with the concentration of 98 percent 2SO4And hydrogen peroxide as described in 7: 3, cleaning for 6min by adopting ultrasonic waves in the mixed solution mixed in the volume ratio;
step 23, placing the gold electrode in absolute ethyl alcohol and cleaning for 6min by adopting ultrasonic waves;
and 24, placing the gold electrode in purified water and cleaning for 6min by adopting ultrasonic waves.
And step 25, respectively taking 5mL of potassium chloride, potassium ferricyanide and potassium ferrocyanide, uniformly mixing the potassium chloride, the potassium ferricyanide and the potassium ferrocyanide to serve as base solutions, placing the gold electrode in the base solutions to perform cyclic voltammetry, and when the peak current is stably maintained at a higher position, indicating that the gold electrode treatment effect is good.
31, preparing 0.1g/L chitosan solution, placing the gold electrode in the step 2 in the solution for 8 hours, and enabling the chitosan 11 to be better gathered on the surface of the gold electrode due to the characteristics of film forming property, biocompatibility and the like of the biomacromolecule chitosan, and enabling the gold electrode to better adsorb the molecularly imprinted polymer due to the sensitization effect of the chitosan; taking out the gold electrode, using N2Blow-drying (to prevent oxidation by air);
and step 32, placing the completely dried gold electrode in a phenol molecular imprinting polymer for soaking for 8 hours, and indirectly gathering the template molecular phenol on the gold electrode to form the imprinting film 12 due to the strong combination effect of the polymer and chitosan. Taking out the gold electrode, using N 2Drying by blowing, and drying the surface of the gold electrode to obtain a polymer modified electrode;
and 33, putting the modified electrode into 0.1mol/LNaOH solution for elution for 20min, neutralizing sodium hydroxide and phenol, removing template molecule phenol, and leaving the specific recognition holes 13 of phenol molecules on the imprinted membrane 12 on the surface of the gold electrode, thus obtaining the phenol molecular imprinting electrochemical sensor.
And meanwhile, preparing a non-imprinted electrochemical sensor, and soaking the gold electrode treated according to the step 2 in the prepared non-imprinted polymer for 8 hours to obtain the non-imprinted electrochemical sensor.
The electrochemical characterization of the performance and mechanism of the molecularly imprinted electrochemical sensor prepared by the present embodiment is described below. The performance of the prepared sensor is characterized by adopting an electrochemical method, and the sensor is detected by using a differential pulse method, a cyclic voltammetry method and an alternating current impedance method to obtain related electric signals, so that the mechanisms on a bare electrode, a phenol imprinting electrode and a non-imprinting electrode can be analyzed. In a three-electrode system, a bare electrode, an imprinted electrode and a non-imprinted electrode are respectively used as working electrodes, AgCl/Ag is used as a reference electrode and platinum is used as an auxiliary electrode to carry out determination under a cyclic voltammetry method. The measurement parameters are as follows: the potential range is selected from-1 to +1V, the sampling interval is set to be 5mV, the scanning speed is 200mV/s, and the sensitivity is 2; 5mL of mixed solution of potassium ferricyanide with the concentration of 5mmol/L, 5mmol/L of potassium ferrocyanide and 0.1mol/L of potassium chloride which are uniformly mixed are weighed and taken as scanning base solution to scan, and different cyclic voltammograms can be obtained. In the same three-electrode system, parameters are changed, a differential pulse method is selected for measurement, the potential range is set to be-0.4-0.6V, the sampling interval is 5mV, the pulse interval is 200mS, the pulse amplitude is 20mV, and the pulse width is 60mS, and the characterization is carried out in the same liquid bottom. Setting the frequency within the range of 0.1-100 kHz, and measuring the process capable of reflecting the electrode interface dynamics by using an alternating current impedance spectrum to measure the impedance of different working electrodes.
Scanning electron microscopy characterization of the phenol molecularly imprinted membrane is described below. And (3) completely drying the prepared imprinted polymer-containing silicon wafer, the prepared non-imprinted polymer silicon wafer and the eluted imprinted polymer silicon wafer, and observing the silicon wafer under a Scanning Electron Microscope (SEM), wherein the working voltage is 5kV, and the current is 10 muA. Comparing the shape difference of the same silicon wafer and different silicon wafers under different magnification; and (3) carrying out suction filtration on the prepared MIP and NIP solution in a suction filter, taking out filter paper, and drying the filter paper in an oven to completely remove water. The polymer solid particles on the filter paper were carefully removed and placed on a conductive gel for observation under a scanning electron microscope. The electron microscope is selected from S-4800, manufactured by Hitachi, Japan.
The sensitivity of the blotting electrode prepared in this embodiment to phenol was measured as follows. Adding 1 mu L of 10-6And (3) placing the mg/L phenol concentrated solution into a base solution, and characterizing different electrodes by adopting a differential pulse method in the base solution by the bare electrode and the eluted blotting electrode. As can be seen from FIG. 2, the bare electrode and the eluted imprinted electrode adsorb phenol molecules in the base solution, and the difference of the peak current between the bare electrode and the eluted imprinted electrode can be seen through a differential pulse diagram. The oxidation peak current of the bare electrode is 4250nA, and the oxidation peak current of the eluted blotting electrode is 2000nA, which shows that the recognition capability of the blotting electrode on phenol is far greater than that of the bare electrode on phenol. The reason is that holes which are specifically identified with phenol are left on the blotting membrane on the eluted blotting electrode, and when phenol molecules exist in the base solution, the phenol molecules enter the holes of the blotting membrane to be specifically combined, so that the holes are filled, and the current oxidation peak is raised. The bare electrode has no phenol-specific identification holes, so that the bare electrode is not sensitive to phenol and has small peak current change. In conclusion, the prepared phenol molecular imprinting electrochemical sensor has strong recognition capability on phenol in a water body, and can be used as an effective method for detecting the content of phenol in a water sample.
The linear relationship and the standard curve of the phenol molecular imprinting electrochemical sensor of the present embodiment are described below. A mixed solution (V) prepared by uniformly mixing 5mmol/L potassium ferricyanide, 5mmol/L potassium ferrocyanide and 0.1mol/L potassium chloride1:V2:V31:1:1) as a scanning base solution, setting the potential range to be-0.4-0.6V, and injecting the base solution with a micro-injector according to a certain volume gradient to the concentration of 0-24.6 multiplied by 10-6In a three-electrode system consisting of mg/L phenol solution, an eluted phenol molecular imprinting electrode as a working electrode, an auxiliary electrode and a reference electrode, performing electrochemical characterization on the imprinting electrode by adopting a differential pulse method to obtain the imprinting electrode adsorbing phenol with different concentrationsDifferential pulse diagram, fig. 3. In the differential pulse diagram of fig. 3, it can be verified again by comparison that the eluted imprinted membrane on the surface of the imprinted electrode is eluted to leave a hole specifically bound with the phenol molecular structure, and as the concentration of the added phenol increases, the imprinted hole is filled, the concentration of effective probe ions which can reach the surface of the electrode decreases, so that the converted electric signal is less, and the peak current decreases. When the concentration of the added phenol reaches a certain value, the peak current does not change any more, and the analysis reason may be that the holes on the electrode blotting membrane are completely filled.
The calibration curve of the response current of phenol is obtained by taking the added phenol with different concentrations as the abscissa and the difference value of the peak current generated by phenol with different concentrations and the peak current generated by phenol without addition as the ordinate, as shown in figure 4. As can be seen from FIG. 4, the phenol molecular imprinting electrochemical sensor has a phenol concentration of 6.7X 10-6~24.6×10-6The linear relation is good in the range of mg/L, and the linear equation is expressed as In-I023.043X-38.04 (wherein I)0Peak current generated without addition of phenol, InPeak current generated for dosing different phenol concentrations), correlation linear coefficient R20.9915, limit of detection:the lowest detection limit of phenol determined by a direct photometric method in the national standard method is 0.064mg/L, and compared with the known molecular imprinting electrochemical sensor, the sensitivity of the prepared molecular imprinting electrochemical sensor to phenol is high.
The reproducibility and stability of the phenol molecular imprinting electrochemical sensor of the present embodiment are described below.
In order to examine the reproducibility of the phenol molecular imprinting electrochemical sensor, under the condition that the experimental conditions are optimized to be optimal, the electrode is placed in a position containing 5 mu L10-6In the scanning base solution of mg/L phenol concentrated solution, a differential pulse method is adopted, and the phenol molecular imprinting electrochemical sensor is continuously measured for 6 times under the same experimental conditions, wherein the relative standard deviation is as follows:
TABLE 1 repeated determination of phenol at the same concentration
It can be seen that the phenol molecular imprinting electrochemical sensor has a relative standard deviation of 2.73% < 5%, so it has good reproducibility. The sensor is tested 3 times in the same experimental condition every day for 10 days continuously, and the result shows that the response value of the current is reduced to 93.7% after five days of measurement, and the current is reduced to 90.3% after 10 days of measurement, so that the sensor has good stability.
The interference of the molecularly imprinted electrochemical sensor of this embodiment is described below.
The prepared blotting electrode after elution was placed in a container containing 3. mu.L of 10-6measuring peak current of the scanned base solution of phenol with mg/L concentration by adopting a differential pulse method, respectively adding formaldehyde, acetone and resorcinol with the same concentration into the base solution, and observing the change value of the added peak current. According to the interference formula K ═ Delta Ir/△I0(wherein. DELTA.I0Peak current variation value,. DELTA.I, produced by adding phenol to the blank concentraterPeak current change value generated by adding an interfering substance to a base solution containing phenol) to determine the degree of interference of the interfering substance. Experiments show that the interference values of formaldehyde, acetone and resorcinol are small. The obtained interference value shows that the holes on the phenol molecular imprinting membrane have specific recognition capability on phenol, the interference resistance on other substances is strong, and the sensor has good selectivity.
TABLE 2 interfering influence of coexisting substances on phenol determination
The sample measurement of the molecularly imprinted electrochemical sensor of the present embodiment is described below. Taking 100ml of water sample of the fragrant lake, filtering and precipitating, then taking 3 mu L of supernatant water sample in the base solution by using a micro-injector, measuring the peak current by adopting a differential pulse method, calculating the difference value between the peak current and the peak current of a blank sample, and substituting the obtained difference value into the calibration curve shown in the figure 4, thereby measuring the content of phenol in the fragrant lake. And (3) taking 10 mu L of phenol concentrated solution with the concentration of 10-6mg/L into the bottom solution containing the water sample, similarly, measuring the peak current of the mixed solution by adopting a differential pulse method, and measuring the phenol content of the mixed solution according to the method, thereby calculating the recovery rate value.
TABLE 3 detection of phenol content in water samples
The phenol content in the water of the fragrant tea lake is measured to be 4.11 multiplied by 10 < -5 > mg/L, and the inspection of the quality standard of the water environment of surface water (GB3838-2002) (see the attached table) shows that the phenol content in the water body does not exceed the standard and accords with the national class I water standard.
The above also applies to instruments such as: a multifunctional micro-electromechanical chemical analyzer (MEC-12B Jiangsu electric analyzer factory); fluorescence microscope (DMI8 come card, Germany).
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (6)
1. The preparation method of the phenol molecular imprinting sensor is characterized by comprising the following steps: it includes:
step 1, preparing a phenol molecularly imprinted polymer;
adding 0.11-0.12 g of phenol and 1.95-2.05 g of acrylamide into 50ml of absolute ethanol, and uniformly mixing the absolute ethanol, the phenol and the acrylamide to prepare a mixed solution; adding 0.45-0.55 g of azobisisobutyronitrile and 0.95-1.05 g of methylene acrylamide into 50ml of absolute ethanol, adding the mixed solution, and uniformly mixing to prepare the phenol molecularly imprinted polymer;
step 2, pretreating a gold electrode;
spreading paste material prepared by mixing aluminum oxide powder and distilled water on the chamois surface, grinding the gold electrode on the chamois surface, and cleaning the surface of the gold electrode with distilled water; placing the treated gold electrode in H with the concentration of 97-99%2SO4And hydrogen peroxide according to the weight ratio of (6-8): 3Volume ofCleaning in the mixed solution mixed in proportion; placing the gold electrode in absolute ethyl alcohol for cleaning; placing the gold electrode in purified water for cleaning;
Step 3, preparing a molecularly imprinted electrochemical sensor;
31, preparing 0.095-0.105 g/L chitosan solution, and placing the gold electrode in the step 2 into the solution to enable the chitosan to be gathered on the surface of the gold electrode; taking out the gold electrode, using N2Drying;
step 32, placing the dried gold electrode in a phenol molecular imprinting polymer for soaking so that the template molecular phenol is indirectly gathered on the gold electrode; taking out the gold electrode, using N2Drying by blowing, and drying the surface of the gold electrode to obtain a polymer modified electrode;
and 33, placing the modified electrode in 0.095-0.105 mol/LNaOH solution for elution, neutralizing sodium hydroxide and phenol, removing template molecule phenol, and leaving specific recognition holes of phenol molecules on an imprinting film on the surface of the gold electrode to obtain the phenol molecular imprinting electrochemical sensor.
2. The method for preparing a phenol molecular imprinting sensor according to claim 1, characterized in that: the step 1 comprises the following steps:
step 11, adding 0.11-0.12 g of phenol and 1.95-2.05 g of acrylamide into 50ml of absolute ethanol, and mixing the absolute ethanol, the phenol and the acrylamide; performing ultrasonic treatment for 25-35 minutes by using an ultrasonic cleaning machine, and standing for 25-35 minutes to uniformly mix to prepare a mixed solution;
Step 12, adding 0.45-0.55 g of azobisisobutyronitrile and 0.95-1.05 g of methylene acrylamide into 50ml of absolute ethanol, adding the mixture into the mixed solution, and mixing; and (3) performing ultrasonic treatment for 25-35 minutes by using an ultrasonic cleaning machine, sealing the solution, and oscillating at the temperature of 22-27 ℃ for 7-9 hours in the oscillating process to uniformly mix to prepare the phenol molecularly imprinted polymer.
3. The method for preparing a phenol molecular imprinting sensor according to claim 1, characterized in that: the step 2 comprises the following steps:
step 21, spreading a pasty material formed by mixing alumina powder and distilled water on the surface of the chamois, and grinding a gold electrode on the surface of the chamois; washing the surface of the gold electrode with distilled water;
step 22, placing the treated gold electrode in H with the concentration of 97-99%2SO4And hydrogen peroxide according to the weight ratio of (6-8): 3, cleaning the mixture in the mixed solution in a volume ratio for 5-7 minutes by adopting ultrasonic waves;
step 23, placing the gold electrode in absolute ethyl alcohol and cleaning for 5-7 minutes by adopting ultrasonic waves;
and 24, placing the gold electrode in purified water and cleaning for 5-7 minutes by adopting ultrasonic waves.
4. The method for preparing a phenol molecular imprinting sensor according to claim 3, characterized in that: this step 21 includes:
Keeping the chamois smooth, and sprinkling a pasty material formed by mixing 0.8-1.2 mu m of aluminum oxide powder and distilled water on the chamois surface; the gold electrode is vertical to the chamois, the surface of the gold electrode needing to be polished is repeatedly polished on the chamois, and the mirror surface is washed by distilled water after polishing;
spreading a paste material prepared by mixing 0.25-0.35 μm aluminum oxide powder and distilled water on the surface of the chamois leather; the gold electrode is vertical to the chamois, the surface of the gold electrode needing to be polished is repeatedly polished on the chamois, and the mirror surface is washed by distilled water after polishing.
5. The method for preparing a phenol molecular imprinting sensor according to claim 3, characterized in that: the step 2 further comprises:
and step 25, taking equal volumes of potassium chloride, potassium ferricyanide and potassium ferrocyanide, uniformly mixing the equal volumes of potassium chloride, potassium ferricyanide and potassium ferrocyanide to serve as a base solution, placing the gold electrode in the base solution for cyclic voltammetry, and when the peak current is stably maintained at a high level, indicating that the gold electrode has a good treatment effect.
6. The method for preparing a phenol molecular imprinting sensor according to claim 1, characterized in that:
in the step 31, the gold electrode in the step 2 is placed in the solution for 7-9 hours;
in the step 32, the blow-dried gold electrode is placed in a phenol molecular imprinting polymer to be soaked for 7-9 hours;
In the step 33, the modified electrode is put into 0.095-0.105 mol/LNaOH solution for elution for 18-22 minutes.
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