CN113804737A - Preparation method of polyaniline-loaded silver/cuprous oxide multi-element nano composite material and modified electrode - Google Patents
Preparation method of polyaniline-loaded silver/cuprous oxide multi-element nano composite material and modified electrode Download PDFInfo
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Abstract
The invention provides a preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nano composite material and a modified electrode, wherein the preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nano composite material comprises the following steps: s1, dispersing aniline monomer in dichloromethane; s2, adding N-methyl pyrrolidone solution and camphorsulfonic acid in sequence under stirring to react at room temperature; s3, adding an ammonium persulfate aqueous solution into the reaction solution, standing for reaction, separating dichloromethane at the lower layer, and filtering the residual solution to obtain a solid product; s4, washing and drying the product to obtain camphorsulfonic acid doped PANI nano powder; s5, dissolving the PANI nano powder in a PBS solution, adding glycol for mixing, adding copper sulfate pentahydrate and a silver acetate solution for fully mixing to obtain a PANI nano composite material precursor solution; and S6, dissolving NaOH and glucose in a PBS solution, adding the precursor solution, mixing, heating, reacting, filtering, cleaning and drying the product after the reaction is finished to obtain the PANI nano composite material powder.
Description
Technical Field
The invention particularly relates to a preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nano composite material and a modified electrode.
Background
Dopamine (DA) plays an important role in the functions of the systems of the human body such as metabolism, central nervous system, cardiovascular system, hormones, kidneys, etc. Abnormal levels of DA can cause neurological disorders such as schizophrenia, parkinson's disease and epilepsy. Uric Acid (UA) is a product of purine metabolism in organisms. UA level abnormalities are associated with a variety of diseases, including Lesch-Nyan disease, intestinal, abdominal and hyperuricemia. The concentration of DA in extracellular fluid of healthy individuals is extremely low (1X 10)-8～1×10-6M), lower DA concentration in extracellular fluid of Parkinson's disease patients (1X 10)-9M). The ability to simultaneously detect DA and UA, biologically important compounds, with high sensitivity, is of great significance in pathological, clinical and biological studies. Therefore, it is necessary to design a strategy for highly sensitive and selective dopamine detection. Many techniques are currently used for the quantitative detection of DA and UA, such as fluorescence, electrochemiluminescence, high performance liquid chromatography, capillary electrophoresis, and electrochemical analysis.
Among them, the electrochemical analysis method has the advantages of high sensitivity, easy miniaturization, low cost, simple preparation and the like, and becomes a hotspot of the current research. However, when the detection is performed using a conventional electrode, the oxidation peak potentials of these biomolecules are almost in the same region. This results in an overlap of their voltammetric responses, and therefore co-existing solutions of DA and UA cannot be tested directly by conventional bare electrodes.
Disclosure of Invention
The invention provides a silver/cuprous oxide nano composite material (PANI-Cu) loaded by polyaniline nano fibers2OAg) and a preparation method of the modified electrode, and is used for high-sensitivity and selective electrochemical detection of DA and UA. The method effectively solves the problems of simultaneous detection of DA and UA, anti-interference performance and sensitivity in the process of detecting DA and UA.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nano composite material comprises the following steps:
s1: adding 0.5mL aniline monomer into 50mL dichloromethane solution, and performing ultrasonic treatment to uniformly disperse the aniline monomer to form transparent and uniform organic phase solution;
s2: adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g of camphorsulfonic acid into the organic phase solution in sequence under the condition of stirring, stirring at room temperature for a preset time, and standing;
s3: slowly adding 5mL of 0.06g/mL ammonium persulfate aqueous solution into the reaction solution prepared by S2, standing for reaction for a preset time, separating lower-layer dichloromethane, and filtering the rest solution through a mixed system filter membrane to obtain a solid product;
s4: cleaning and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: ultrasonically dissolving 400mg of camphorsulfonic acid doped PANI nano powder in 5ml of 0.1M PBS solution, adding 25ml of glycol, fully mixing, adding preset amount of copper sulfate pentahydrate and silver acetate solution, and fully mixing to obtain PANI nano composite material precursor solution;
s6: dissolving 0.1g of NaOH and 3g of glucose in 5ml of 0.1M PBS solution, adding the solution into the PANI nano composite material precursor solution, uniformly mixing, heating at 120 ℃ for reaction for a preset time, filtering a product after the reaction through a mixed system filter membrane, and cleaning and drying a solid product obtained by filtering to obtain PANI nano composite material powder.
As a further improvement, 75mg of copper sulfate pentahydrate and 3.77ml of 47.93mM silver acetate solution were added specifically to S5.
The invention also provides a preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nano composite material modified electrode, which comprises the following steps:
1): polishing a glassy carbon electrode on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, then washing with distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use;
2): adding 2mg of the PANI nano composite material powder prepared by the method and 10 mul of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniformly mixed suspension;
3): and dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing to obtain the PANI nano composite material modified electrode.
As a further improvement, the preparation method of the polyaniline-supported silver/cuprous oxide multi-element nanocomposite modified electrode further comprises the steps of sweeping the prepared PANI nanocomposite modified electrode for 2 hours under the conditions of 0.1M PBS (pH 6.8) and-0.1V-0.9V (vs. sce), and then scanning for 30min under the condition of 0V at constant potential; after repeating the above operation 3 times, the treated modified electrode was immersed in a 0.1M PBS solution for use.
The invention further provides a polyaniline-loaded silver/cuprous oxide multi-element nano composite material modified electrode prepared based on the preparation method, and the test environment is as follows: the PANI nano composite material modified electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Saturated Calomel Electrode (SCE) is used as a reference electrode, a pulse volt-ampere (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, the pulse width is 50ms, and the DPV test is carried out in 0.1M PBS (phosphate buffered saline) solution with the pH value of 6.8.
As a further improvement, the modified electrode was potentiostatically scanned at 0V for 30s before each DPV test.
The invention has the beneficial effects that: the electrode modified by the PANI nano composite material prepared by the invention can realize the simultaneous detection of DA and UA concentrations in DA and UA coexisting liquid; the detection limit of the modified electrode to DA is 0.005 μ M, the detection limit to UA is 1 μ M, and DA and UA are in PANI-Cu in DPV test2The OAg modified electrode has obvious electrochemical response signals and excellent detection sensitivity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is an SEM image of PANI-based series of nano-catalysts.
FIG. 2 shows PANI-Cu2DPV test plots of OAg nanocatalyst-modified electrodes in 0.1M PBS (pH 6.8) containing 1mM UA, 2mM AA, and 200. mu.M DA.
FIG. 3 is a DPV test plot of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) containing 200. mu.M DA.
FIG. 4 is a DPV test plot of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) containing 1mM UA.
FIG. 5 shows PANI-Cu2DPV test plots of OAg-modified electrodes in 0.1M PBS (pH 6.8) solutions containing different concentrations of DA.
FIG. 6 shows DA in PANI-Cu2Standard curve for DPV test on OAg modified electrodes.
FIG. 7 shows PANI-Cu2DPV test plots of OAg-modified electrodes in 0.1M PBS (pH 6.8) solutions containing different concentrations of UA.
FIG. 8 shows UA in PANI-Cu2Standard curve for DPV test on OAg modified electrodes.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the invention provides a preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nano composite material, which comprises the following steps:
s1: adding 0.5mL aniline monomer into 50mL dichloromethane solution, and performing ultrasonic treatment to uniformly disperse the aniline monomer to form transparent and uniform organic phase solution;
s2: adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g of camphorsulfonic acid into the organic phase solution in sequence under the condition of stirring, stirring at room temperature for a preset time, and standing;
s3: slowly adding 5mL of 0.06g/mL ammonium persulfate aqueous solution into the reaction solution prepared by S2, standing for reaction for a preset time, separating lower-layer dichloromethane, and filtering the rest solution through a mixed system filter membrane to obtain a solid product;
s4: cleaning and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: ultrasonically dissolving 400mg of camphorsulfonic acid doped PANI nano powder in 5ml of 0.1M PBS solution, adding 25ml of glycol, fully mixing, adding preset amount of copper sulfate pentahydrate and silver acetate solution, and fully mixing to obtain PANI nano composite material precursor solution;
s6: dissolving 0.1g of NaOH and 3g of glucose in 5ml of 0.1M PBS solution, adding the solution into the PANI nano composite material precursor solution, uniformly mixing, heating at 120 ℃ for reaction for a preset time, filtering a product after the reaction through a mixed system filter membrane, and cleaning and drying a solid product obtained by filtering to obtain PANI nano composite material powder.
As a further improvement, 75mg of copper sulfate pentahydrate and 3.77ml of 47.93mM silver acetate solution were added specifically to S5.
As a further improvement, the stirring time at room temperature in S2 is 20-30 min.
As a further improvement, the standing reaction time in S3 is 60-90 min.
As a further improvement, the specific steps of S4 are: washing the solid product with distilled water and ethanol in sequence, and filtering to obtain the final product, and naturally drying to obtain the camphorsulfonic acid doped PANI nano powder.
As a further improvement, the heating reaction time in S6 is 3-4 h; the specific steps of cleaning and drying the solid product in the S6 are as follows: and (4) filtering to obtain a solid product, washing with pure water and ethanol, and naturally airing to obtain PANI nano composite material powder.
The embodiment further provides a preparation method of the polyaniline-supported silver/cuprous oxide multi-element nanocomposite modified electrode, which comprises the following steps:
1): polishing a glassy carbon electrode on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, then washing with distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use;
2): adding 2mg of the PANI nano composite material powder prepared by the method and 10 mul of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniformly mixed suspension;
3): and dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing to obtain the PANI nano composite material modified electrode.
As a further improvement, the preparation method of the polyaniline-supported silver/cuprous oxide multi-element nanocomposite modified electrode further comprises the steps of sweeping the prepared PANI nanocomposite modified electrode for 2 hours under the conditions of 0.1M PBS (pH 6.8) and-0.1V-0.9V (vs. sce), and then scanning for 30min under the condition of 0V at constant potential; repeating the operation for 3 times, and soaking the treated modified electrode in 0.1M PBS solution for later use; namely, the prepared catalyst modified electrode is pretreated to obtain a stable electrochemical detection signal with good repeatability in the electrochemical test process.
The polyaniline-loaded silver/cuprous oxide multi-element nano composite material modified electrode prepared based on the preparation method has the test environment that: the PANI nano composite material modified electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Saturated Calomel Electrode (SCE) is used as a reference electrode, a pulse volt-ampere (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, the pulse width is 50ms, and the DPV test is carried out in 0.1M PBS (phosphate buffered saline) solution with the pH value of 6.8. Before each DPV test, scanning the modified electrode at a constant potential for 30s under the condition of 0V to enable the modified electrode material to be in an electrochemical reduction state so as to obtain a stable and high-sensitivity electrochemical signal.
Example 1
50mL of methylene chloride was added to a round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and uniformly dispersed by sonication to form a clear and homogeneous solution of the organic phase. The obtained organic phase solution was placed on a magnetic stirrer, 50mL of 0.2mol/L N-methylpyrrolidone aqueous solution was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of the round-bottom flask, and after the dichloromethane reaction solution is kept standing for 60 minutes, the lower layer of dichloromethane is sucked out by a rubber head dropper and poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
And (2) ultrasonically dissolving 400mg of camphorsulfonic acid doped PANI powder in 5ml of 0.1M PBS solution, adding 25ml of ethylene glycol, stirring, ultrasonically and fully mixing, adding 75mg of blue vitriol and 3.77ml of 47.93mM silver acetate solution, and fully mixing to obtain a PANI nano composite material precursor solution. And adding 0.1g of NaOH and 3g of glucose into 5ml of 0.1M PBS solution, stirring or ultrasonically dissolving, adding into the PANI nano composite material precursor solution, uniformly mixing, transferring to a hydrothermal reaction kettle, and heating at 120 ℃ for 3 hours. After the reaction is finished, filtering the solid product by using a mixed system filter membrane with the aperture of 0.22 mu m, washing by using pure water and ethanol, and naturally airing to obtain the PANI nano composite material (PANI-Cu)2OAg) powder.
And polishing a glassy carbon electrode with the diameter of 5mm on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, washing by using distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use. 2mg of PANI nano composite material powder and 10 mul of 5% Nafion ethanol solution are dispersed in 0.5ml of ethanol and subjected to ultrasonic treatment for 30min to form a uniformly mixed suspension. And dripping 20 mu l of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain a stable and well-repeatable electrochemical detection signal, a prepared catalyst modified electrode needs to be pretreated, namely, Cyclic Voltammetry (CV) is swept for 2 hours in 0.1M PBS (pH 6.8) under the condition of a potential range of-0.1V-0.9V (vs. SCE), and then constant potential scanning is carried out for 30min under the condition of 0V; after repeating the above operation 3 times, the pretreated modified electrode was immersed in 0.1M PBS solution for use.
The electrochemical test adopts a three-electrode system, wherein a PANI nano composite material modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode, so that a pulse volt-ampere (DPV) test is carried out. The potential range for the DPV test was-0.1V-0.9V (vs. SCE), the scan amplitude was 50mV, and the pulse width was 50 ms. In order to obtain a stable and highly sensitive electrochemical signal, before each DPV test, the modified electrode is scanned at a constant potential for 30s under the condition of 0V so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in the presence of phosphate buffered saline (0.1M PBS solution, pH 6.8).
Comparative example 1
50mL of methylene chloride was added to a round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and uniformly dispersed by sonication to form a clear and homogeneous solution of the organic phase. The obtained organic phase solution was placed on a magnetic stirrer, 50mL of 0.2mol/L N-methylpyrrolidone aqueous solution was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of the round-bottom flask, and after the dichloromethane reaction solution is kept standing for 60 minutes, the lower layer of dichloromethane is sucked out by a rubber head dropper and poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
And polishing a glassy carbon electrode with the diameter of 5mm on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, washing by using distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use. 2mg of PANI nano powder and 10. mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And dripping 20 mu l of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain a stable and well-repeatable electrochemical detection signal, a prepared catalyst modified electrode needs to be pretreated, namely, Cyclic Voltammetry (CV) is swept for 2 hours in 0.1M PBS (pH 6.8) under the condition of a potential range of-0.1V-0.9V (vs. SCE), and then constant potential scanning is carried out for 30min under the condition of 0V; after repeating the above operation 3 times, the pretreated modified electrode was immersed in 0.1M PBS solution for use.
The electrochemical experiment adopts a three-electrode system, wherein a PANI modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode, so that a pulse volt-ampere (DPV) test is carried out. The potential range for the DPV test was-0.1V-0.9V (vs. SCE), the scan amplitude was 50mV, and the pulse width was 50 ms. In order to obtain a stable and highly sensitive electrochemical signal, before each DPV test, the modified electrode is scanned at a constant potential for 30s under the condition of 0V so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in the presence of phosphate buffered saline (0.1M PBS solution, pH 6.8).
Comparative example 2
50mL of methylene chloride was added to a round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and uniformly dispersed by sonication to form a clear and homogeneous solution of the organic phase. The obtained organic phase solution was placed on a magnetic stirrer, 50mL of 0.2mol/L N-methylpyrrolidone aqueous solution was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of the round-bottom flask, and after the dichloromethane reaction solution is kept standing for 60 minutes, the lower layer of dichloromethane is sucked out by a rubber head dropper and poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
Dissolving 400mg camphorsulfonic acid doped PANI powder in 5ml 0.1M PBS solution by ultrasonic, adding 25ml ethylene glycol, stirring, ultrasonic mixing, adding 0.15g blue vitriol, mixing to obtain PANI-Cu2And (4) O precursor solution. Adding 0.1g NaOH and 3g glucose into 5ml 0.1M PBS solution, stirring or ultrasonic dissolving, and adding the PANI-Cu2And (3) uniformly mixing the O precursor solution, transferring the mixture to a hydrothermal reaction kettle, and heating the mixture for 3 hours at the temperature of 120 ℃. After the reaction is finished, filtering the solid product by using a mixed system filter membrane with the aperture of 0.22 mu m, washing by using pure water and ethanol, and naturally airing to obtain PANI-Cu2And (3) O powder.
And polishing a glassy carbon electrode with the diameter of 5mm on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, washing by using distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use. 2mg of PANI-Cu2O powder and 10. mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a uniformly mixed suspension. And dripping 20 mu l of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain a stable and well-repeatable electrochemical detection signal, a prepared catalyst modified electrode needs to be pretreated, namely, Cyclic Voltammetry (CV) is swept for 2 hours in 0.1M PBS (pH 6.8) under the condition of a potential range of-0.1V-0.9V (vs. SCE), and then constant potential scanning is carried out for 30min under the condition of 0V; after repeating the above operation 3 times, the pretreated modified electrode was immersed in 0.1M PBS solution for use.
The electrochemical test adopts a three-electrode system in which PANI-Cu is adopted2And the O modified electrode is a working electrode, the graphite electrode is a counter electrode, and the Saturated Calomel Electrode (SCE) is a reference electrode, and a pulse volt-ampere (DPV) test is carried out. The potential range for the DPV test was-0.1V-0.9V (vs. SCE), the scan amplitude was 50mV, and the pulse width was 50 ms. In order to obtain stable and highly sensitive electricityChemical signals, before each DPV test, the modified electrode is scanned for 30s under the condition of constant potential of 0V, so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in the presence of phosphate buffered saline (0.1M PBS solution, pH 6.8).
Comparative example 3
50mL of methylene chloride was added to a round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and uniformly dispersed by sonication to form a clear and homogeneous solution of the organic phase. The obtained organic phase solution was placed on a magnetic stirrer, 50mL of 0.2mol/L N-methylpyrrolidone aqueous solution was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of the round-bottom flask, and after the dichloromethane reaction solution is kept standing for 60 minutes, the lower layer of dichloromethane is sucked out by a rubber head dropper and poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
And (2) ultrasonically dissolving 400mg of camphorsulfonic acid doped PANI powder in 5ml of 0.1M PBS solution, adding 25ml of ethylene glycol, stirring, ultrasonically and fully mixing, then, fully mixing 7.54ml of 47.93mM silver acetate solution, and fully mixing to obtain a PANI-Ag precursor solution. And adding 0.1g of NaOH and 3g of glucose into 5ml of 0.1M PBS solution, stirring or ultrasonically dissolving, adding into the PANI-Ag precursor solution, uniformly mixing, transferring to a hydrothermal reaction kettle, and heating at 120 ℃ for 3 hours. After the reaction is finished, filtering the solid product by using a mixed system filter membrane with the aperture of 0.22 mu m, washing by using pure water and ethanol, and naturally airing to obtain PANI-Ag powder.
And polishing a glassy carbon electrode with the diameter of 5mm on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, washing by using distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use. 2mg of PANI-Ag powder and 10. mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And dripping 20 mu l of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain a stable and well-repeatable electrochemical detection signal, a prepared catalyst modified electrode needs to be pretreated, namely, Cyclic Voltammetry (CV) is swept for 2 hours in 0.1M PBS (pH 6.8) under the condition of a potential range of-0.1V-0.9V (vs. SCE), and then constant potential scanning is carried out for 30min under the condition of 0V; after repeating the above operation 3 times, the pretreated modified electrode was immersed in 0.1M PBS solution for use.
The electrochemical test adopts a three-electrode system, wherein a PANI-Ag modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode, so that a pulse volt-ampere (DPV) test is carried out. The potential range for the DPV test was-0.1V-0.9V (vs. SCE), the scan amplitude was 50mV, and the pulse width was 50 ms. In order to obtain a stable and highly sensitive electrochemical signal, before each DPV test, the modified electrode is scanned at a constant potential for 30s under the condition of 0V so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in the presence of phosphate buffered saline (0.1M PBS solution, pH 6.8).
Test example:
FIG. 1 is an SEM image of a PANI-based series of nano-catalysts; as can be seen from the figure, the PANI nano-carrier is of a short fiber structure, and the diameter is 30-60 nm; PANI-Cu synthesized by hydrothermal method2O nano catalyst, Cu2O presents 100-300nm irregular particles and is loaded on the PANI surface; the PANI-Ag nano catalyst synthesized by a hydrothermal method has an Ag structure of long-chain beads with the diameter of about 100 nm; after the multi-component material is compounded, Cu2The OAg nano material combines Cu in shape2The O and Ag nano material is characterized by presenting a slender ellipsoidal structure. By EDS characterization, PANI-Cu2The elongated ellipsoidal nano material loaded in the OAg nano catalyst is Cu2OAg bicomponent materials, in which Cu2O: the mass ratio of Ag is 1: 1. PANI-Cu2OAg、PANI-Cu2O, PANI-Ag contains metal or metal oxide with a total loading mass of 10%.
FIG. 2 shows PANI-Cu2The OAg nanocatalyst modified electrode was dissolved in 0.1M PBS (pH 6.8) containing 1mM UA, 2mM AA, 200. mu.M DADPV test patterns in liquid; as can be seen from the graph, the oxidation current potential of DA ranges from 0.04V to 0.4V, and the oxidation peak potential is 0.17V; the oxidation current potential range of UA is 0.22V-0.64V, and the oxidation peak is 0.4V; AA did not have a significant electrochemical response signal under the test conditions. Therefore, in the system detection with coexistence of DA, UA and AA, the test method has better sensitivity and anti-interference capability to DA and UA.
FIG. 3 is a DPV test plot of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) containing 200. mu.M DA; it can be seen from the figure that there is a large difference between the oxidation peak potential and the oxidation current potential range of DA on the PANI-based modified electrode. In terms of detection sensitivity, DA is in PANI-Cu2The electrochemical response signal on the OAg modified electrode is obviously larger than PANI-Cu2O, PANI-Ag and PANI modified electrode shows excellent electro-catalytic performance to DA.
FIG. 4 is a DPV test plot of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) containing 1mM UA; as can be seen from the figure, the UA has larger difference in the oxidation current potential range and the oxidation peak potential on the PANI-based series modified electrode. In the series of modified electrodes, UA is in PANI-Cu2Comparison of electrochemical response signals on OAg modified electrodes with PANI-Cu2O, PANI-Ag and PANI modified electrodes show great enhancement and excellent electrocatalysis performance. Thus, PANI-Cu2The OAg modified electrode has excellent electrocatalytic performance for DA and UA.
FIG. 5 shows PANI-Cu2DPV test plots of OAg modified electrodes in 0.1M PBS (pH 6.8) solutions containing different concentrations of DA; as can be seen from the figure, the oxidation current potentials of different concentrations of DA on the modified electrode are all in the range of 0.04V-0.4V, and the oxidation peak potentials are all around 0.17V; as the concentration of DA increases, the electrochemical response signal of DA on the modified electrode also increases, and the detection limit is 0.005 mu M. The concentration of DA in the extracellular fluid of a healthy individual is 0.01 to 1 μ M, while the normal concentration of DA in urine is 0.1 to 2 μ M. Therefore, the DA detection method provided by the invention has high enough sensitivity, can accurately detect the DA concentration in human body fluid, and is not interfered by UA and AA.
FIG. 6 shows DA in PANI-Cu2Standard curve for DPV test on OAg modified electrode; as can be seen from the graph, in the concentration range of 0.005. mu.M to 200. mu.M detected in the present invention, a bilinear relationship is exhibited between the DA concentration and the peak current. The linear curve at high concentration (10-200. mu.M) is 0.0608x +2.0275, and the correlation coefficient R is20.99771. The linear curve at low concentration (0.005 mu M-10 mu M) is y-0.204 x +0.364, and the correlation coefficient R is2＝0.94276。
FIG. 7 shows PANI-Cu2DPV test plots of OAg-modified electrodes in 0.1M PBS (pH 6.8) solutions containing different concentrations of UA; as can be seen from the figure, the oxidation current potentials of different concentrations of UA on the modified electrode are all in the range of 0.22V-0.64V, and the oxidation peak potentials are all around 0.4V; as the concentration of UA increases, the electrochemical response signal of UA on the modified electrode also increases, and the detection limit is 1 mu M. The UA concentration in the serum of a healthy human body is generally 120-460 mu M, and the method provided by the invention has enough sensitivity to be used for detecting UA in the serum of the human body and is not interfered by DA and AA.
FIG. 8 shows UA in PANI-Cu2Standard curve for DPV test on OAg modified electrodes. As can be seen from the figure, in the range of the linear concentration detected by the invention, 1 muM-500 muM, the UA concentration and the peak current have a linear relation, the linear curve is that y is 0.0211x +0.6490, and the correlation coefficient is R2＝0.99138。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nano composite material is characterized by comprising the following steps:
s1: adding 0.5mL aniline monomer into 50mL dichloromethane solution, and performing ultrasonic treatment to uniformly disperse the aniline monomer to form transparent and uniform organic phase solution;
s2: adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g of camphorsulfonic acid into the organic phase solution in sequence under the condition of stirring, stirring at room temperature for a preset time, and standing;
s3: slowly adding 5mL of 0.06g/mL ammonium persulfate aqueous solution into the reaction solution prepared by S2, standing for reaction for a preset time, separating lower-layer dichloromethane, and filtering the rest solution through a mixed system filter membrane to obtain a solid product;
s4: cleaning and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: ultrasonically dissolving 400mg of camphorsulfonic acid doped PANI nano powder in 5ml of 0.1M PBS solution, adding 25ml of glycol, fully mixing, adding preset amount of copper sulfate pentahydrate and silver acetate solution, and fully mixing to obtain PANI nano composite material precursor solution;
s6: dissolving 0.1g of NaOH and 3g of glucose in 5ml of 0.1M PBS solution, adding the solution into the PANI nano composite material precursor solution, uniformly mixing, heating at 120 ℃ for reaction for a preset time, filtering a product after the reaction through a mixed system filter membrane, and cleaning and drying a solid product obtained by filtering to obtain PANI nano composite material powder.
2. The preparation method of the polyaniline-supported silver/cuprous oxide multi-element nanocomposite material 1 is characterized in that 75mg of copper sulfate pentahydrate and 3.77ml of 47.93mM silver acetate solution are specifically added into S5.
3. The preparation method of the polyaniline-supported silver/cuprous oxide multi-element nano composite material according to 2 is characterized in that the stirring time at room temperature in S2 is 20-30 min.
4. The preparation method of the polyaniline-supported silver/cuprous oxide multi-element nano composite material according to 2 is characterized in that the standing reaction time in S3 is 60-90 min.
5. The preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite material according to 2 is characterized in that the specific step of S4 is as follows: washing the solid product with distilled water and ethanol in sequence, and filtering to obtain the final product, and naturally drying to obtain the camphorsulfonic acid doped PANI nano powder.
6. The preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nano composite material according to 2 is characterized in that the heating reaction time in S6 is 3-4 h; the specific steps of cleaning and drying the solid product in the S6 are as follows: and (4) filtering to obtain a solid product, washing with pure water and ethanol, and naturally airing to obtain PANI nano composite material powder.
7. A preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nano composite material modified electrode is characterized by comprising the following steps:
1): polishing a glassy carbon electrode on a polishing pad by using alumina slurry with the grain diameters of 3 microns, 1 micron, 0.3 micron and 0.05 micron in sequence, then washing with distilled water, ultrasonically cleaning in absolute ethyl alcohol and distilled water respectively, and airing for later use;
2): adding 2mg of PANI nano composite material powder prepared by any one method of claims 1 to 6 and 10 mul of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
3): and dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing to obtain the PANI nano composite material modified electrode.
8. The preparation method of the polyaniline-supported silver/cuprous oxide multi-element nanocomposite modified electrode according to 7 is characterized by further comprising the steps of conducting Cyclic Voltammetry (CV) sweep on the prepared PANI nanocomposite modified electrode for 2 hours under the conditions of 0.1M PBS (pH 6.8) and potential range of-0.1V-0.9V (vs. SCE), and then conducting constant potential sweep for 30min under the condition of 0V; after repeating the above operation 3 times, the treated modified electrode was immersed in a 0.1M PBS solution for use.
9. A polyaniline-supported silver/cuprous oxide multi-element nanocomposite modified electrode, wherein the polyaniline-supported silver/cuprous oxide multi-element nanocomposite modified electrode is prepared by the method of any of claims 7-8; the electrochemical test environment is as follows: the PANI nano composite material modified electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Saturated Calomel Electrode (SCE) is used as a reference electrode, a pulse volt-ampere (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, the pulse width is 50ms, and the DPV test is carried out in 0.1M PBS (phosphate buffered saline) solution with the pH value of 6.8.
10. The polyaniline-supported silver/cuprous oxide nanocomposite modified electrode of claim 9, wherein before each DPV test, the modified electrode is scanned potentiostatically at 0V for 30 s.
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