CN113804738B - Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof - Google Patents

Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof Download PDF

Info

Publication number
CN113804738B
CN113804738B CN202110991182.3A CN202110991182A CN113804738B CN 113804738 B CN113804738 B CN 113804738B CN 202110991182 A CN202110991182 A CN 202110991182A CN 113804738 B CN113804738 B CN 113804738B
Authority
CN
China
Prior art keywords
pani
electrode
solution
stirring
polyaniline
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
Application number
CN202110991182.3A
Other languages
Chinese (zh)
Other versions
CN113804738A (en
Inventor
刘锡尧
赵文昌
应少明
李萍
林玲玲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningde Normal University
Original Assignee
Ningde Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ningde Normal University filed Critical Ningde Normal University
Priority to CN202110991182.3A priority Critical patent/CN113804738B/en
Publication of CN113804738A publication Critical patent/CN113804738A/en
Application granted granted Critical
Publication of CN113804738B publication Critical patent/CN113804738B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

The invention provides a polyaniline-loaded cuprous oxide sensing electrode and a preparation method thereof, comprising the following steps: s1, dispersing aniline monomer in dichloromethane; s2, adding an N-methyl pyrrolidone aqueous solution and camphorsulfonic acid in sequence under the stirring condition to react at room temperature; s3, slowly 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, cleaning and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder; s5, dispersing camphorsulfonic acid doped PANI nano powder in glycol solution, sequentially adding copper sulfate pentahydrate, PVP, sodium hydroxide solution and glucose aqueous solution for stirring reaction, continuously stirring reaction at 80 ℃ after the reaction, filtering, washing and drying the product after the reaction is finished to obtain PANI-Cu 2 O nano powder; then PANI-Cu is used 2 And modifying the glassy carbon electrode by the O nano powder to obtain the polyaniline-loaded cuprous oxide sensing electrode.

Description

Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof
Technical Field
The invention particularly relates to a polyaniline-loaded cuprous oxide sensing electrode and a preparation method thereof.
Background
Dopamine (DA) is an important neurotransmitter in the mammalian central nervous system. Low levels of DA can cause neurological dysfunction such as parkinson's disease, schizophrenia, etc. Thus, DA is a hotspot of current neurological and chemist research, and the development of a rapid and simple method for measuring DA concentration is also an important concern for current researchers. Uric Acid (UA) is the main end product of purine metabolism. Studies have shown that extremely abnormal UA levels are closely associated with several diseases, such as gout, hyperuricemia, and Lesch-Nyan disease. Since UA and DA are often present in both extracellular fluid and blood of the central nervous system, it is of great importance to detect both DA and UA in routine assays.
The main testing methods of DA and UA at present include various analysis techniques such as ultraviolet visible spectrophotometry, fluorescence method, chemiluminescence method, high performance liquid chromatography and the like. However, these methods are complicated to operate, high in cost and long in time consumption, and their low detection sensitivity also limits their clinical application. Since DA and UA have electrochemical activity, their electrochemical detection methods are the hot spot of current research. However, since the structures of DA and UA molecules are relatively similar, oxidation peaks on the conventional bare electrode overlap, and the conventional bare electrode cannot be used for testing.
Disclosure of Invention
The invention provides polyaniline-loaded cuprous oxide (PANI-Cu) 2 O) DA and UA selective electrochemical detection electrode and preparation method thereof can effectively solve the problems of DA and UA simultaneous detection, anti-interference and sensitivity.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a polyaniline-loaded cuprous oxide sensing electrode comprises the following steps:
s1: adding 0.5mL of aniline monomer into 50mL of dichloromethane solution, and carrying out ultrasonic treatment to uniformly disperse the aniline monomer to form transparent uniform organic phase solution;
s2: sequentially adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g camphorsulfonic acid into the organic phase solution under the stirring condition, 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 in the step S2, standing for reaction for a preset time, separating the lower dichloromethane layer, and filtering the residual solution through a mixed system filter membrane to obtain a solid product;
s4: washing and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: 160mg of camphorsulfonic acid doped PANI nano powder is mixed with 50ml of ethylene glycolDispersing in alcohol solution by ultrasonic, adding 0.25g of copper sulfate pentahydrate and 0.04g of PVP, stirring, then dropwise adding 25ml of 0.09M sodium hydroxide aqueous solution, stirring, adding 25ml of 1.3M glucose aqueous solution after stirring for a preset time, stirring for a period of time, reacting for 1-2h at 80 ℃, filtering the product by a mixed filter membrane after the reaction is finished, washing the filtered solid product, and drying to obtain PANI-Cu 2 O nano powder;
s6: polishing the glassy carbon electrode on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use;
s7: 2mg of PANI-Cu 2 Adding O nano powder and 10 mu l of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
s8: dripping 20 μl of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and air drying at room temperature to obtain PANI-Cu 2 O modifies the electrode.
As a further improvement, the preparation method of the polyaniline-loaded cuprous oxide sensing electrode further comprises the steps of preparing the PANI-Cu 2 The O modified electrode is subjected to Cyclic Voltammetry (CV) scanning for 2 hours under the condition of 0.1M PBS (pH 6.8) and the potential range of-0.1V to 0.9V (vs. SCE), and then is subjected to constant potential scanning for 30 minutes under the condition of 0V; after repeating the above operation 3 times, the modified electrode after the treatment was immersed in a 0.1M PBS solution for use.
The invention also provides a polyaniline-loaded cuprous oxide sensing electrode prepared based on the preparation method, and the test environment is as follows: with PANI-Cu 2 The O modified electrode is a working electrode, the graphite electrode is a counter electrode, the Saturated Calomel Electrode (SCE) is a reference electrode, a pulse voltammetry (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. Wherein the DPV test was performed in 0.1M PBS solution at ph=6.8.
As a further improvement, the modified electrode was potentiostatic scanned at 0V for 30s prior to each DPV test.
The invention is characterized in thatThe beneficial effects are that: PANI-Cu prepared by the invention 2 The O modified electrode can effectively solve the problem that DA and UA oxidation peaks are overlapped and are difficult to detect, and can realize the simultaneous detection of DA and UA; in addition, the detection limit of the modified electrode to DA is 0.001 mu M (which is expected to be used for detecting the DA content in extracellular fluid of a Parkinson patient); the detection limit of UA is 1 mu M, and has higher sensitivity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows PANI and PANI-Cu 2 SEM image of O nanocatalyst.
FIG. 2 shows PANI-Cu 2 DPV test pattern of O nanocatalyst modified electrode in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA.
FIG. 3 shows PANI and PANI-Cu 2 DPV test comparison plot of O nanocatalyst modified electrode in 0.1M PBS (pH 6.8) solution containing 200. Mu.M DA (A) and 1mM UA (B).
FIG. 4 shows PANI-Cu 2 DPV test patterns of O modified electrodes in 0.1M PBS (pH 6.8) solutions containing different concentrations of DA.
FIG. 5 shows DA in PANI-Cu 2 Standard curve for DPV test on O-modified electrode.
FIG. 6 is a PANI-Cu 2 DPV test patterns of O modified electrodes in 0.1M PBS (pH 6.8) solutions containing various concentrations of UA.
FIG. 7 shows UA in PANI-Cu 2 Standard curve for DPV test on O-modified electrode.
Detailed Description
For the purpose of making 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 clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as 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, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
The embodiment of the invention provides a preparation method of a polyaniline-loaded cuprous oxide sensing electrode, which comprises the following steps:
s1: adding 0.5mL of aniline monomer into 50mL of dichloromethane solution, and carrying out ultrasonic treatment to uniformly disperse the aniline monomer to form transparent uniform organic phase solution;
s2: sequentially adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g camphorsulfonic acid into the organic phase solution under the stirring condition, 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 in the step S2, standing for reaction for a preset time, separating the lower dichloromethane layer, and filtering the residual solution through a mixed system filter membrane to obtain a solid product;
s4: washing and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: dispersing 160mg of camphorsulfonic acid doped PANI nano powder in 50ml of glycol solution by ultrasonic, adding 0.25g of cupric sulfate pentahydrate and 0.04g of PVP, stirring, adding 25ml of 0.09M sodium hydroxide aqueous solution dropwise, stirring for a preset time, adding 25ml of 1.3M glucose aqueous solution, stirring for a period of time, stirring at 80 ℃ for reaction for 1-2h, filtering the product after the reaction is finished by a mixed system filter membrane, washing the filtered product to obtain a solid product, and drying to obtain PANI-Cu 2 O nano powder;
s6: polishing the glassy carbon electrode on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use;
s7: 2mg of PANI-Cu 2 Adding O nano powder and 10 mu l of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
s8: dripping 20 μl of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and air drying at room temperature to obtain PANI-Cu 2 O modifies the electrode.
As a further improvement, the preparation method of the polyaniline-loaded cuprous oxide sensing electrode further comprises the steps of preparing the PANI-Cu 2 The O modified electrode is subjected to Cyclic Voltammetry (CV) scanning for 2 hours under the condition of 0.1M PBS (pH 6.8) and the potential range of-0.1V to 0.9V (vs. SCE), and then is subjected to constant potential scanning for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, immersing the treated modified electrode in 0.1M PBS solution for standby, i.e. pretreating the prepared catalyst modified electrode to obtain stable and better-repeatability electrochemical detection signals in the electrochemical test process.
As a further improvement, the stirring time at room temperature in S2 is 20-30min.
As a further improvement, the standing reaction time in S3 is 60-90min.
As a further improvement, the specific steps of S4 are: washing the solid product with distilled water and ethanol in turn, cleaning the filtered product, and naturally airing to obtain camphorsulfonic acid doped PANI nano powder.
As a further improvement, adding copper sulfate pentahydrate and PVP into S5, and stirring for 30min; dropwise adding sodium hydroxide aqueous solution and stirring for 20-30min; adding glucose aqueous solution, and stirring for 20-30min.
As a further improvement, the solid product in S5 is washed and dried by the following steps: washing the solid product with absolute ethanol and pure water for 4-6 times, and naturally air drying to obtain PANI-Cu 2 O nanometer powder.
Based on the upper partThe polyaniline-loaded cuprous oxide sensing electrode prepared by the preparation method has the following testing environment: with PANI-Cu 2 The O modified electrode is a working electrode, the graphite electrode is a counter electrode, the Saturated Calomel Electrode (SCE) is a reference electrode, a pulse voltammetry (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. Wherein the DPV test was performed in 0.1M PBS solution at ph=6.8. Before each DPV test, the modified electrode is scanned for 30s under the condition of 0V to make the modified electrode material in electrochemical reduction state so as to obtain stable and high-sensitivity electrochemical signal.
Example 1
50mL of methylene chloride was added to the round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and dispersed uniformly by sonication to form a clear and homogeneous organic phase solution. The resulting organic phase solution was placed on a magnetic stirrer, 50mL of a 0.2mol/L aqueous solution of N-methylpyrrolidone 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 a round-bottom flask, after the standing reaction is carried out for 60 minutes, the lower dichloromethane layer is sucked out by a rubber head dropper and is 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.
Taking 160mg of camphorsulfonic acid doped polyaniline powder, dispersing in 50ml of glycol solution by ultrasonic, adding 0.25g of cupric sulfate pentahydrate and 0.04g of PVP, stirring for 30min, then dropwise adding 25ml of 0.09M sodium hydroxide aqueous solution, stirring for 20min, adding 25ml of 1.3M glucose aqueous solution, stirring for 20min, transferring to a water bath kettle, and stirring for reaction for 1h at 80 ℃. Filtering the solid product with a 0.22 μm pore diameter mixed filter membrane, washing with anhydrous ethanol and pure water for 4-6 times, and naturally air drying to obtain PANI-Cu 2 O nanometer powder.
Sequentially arranging glassy carbon electrodes with diameters of 5mmPolishing with alumina slurries with particle diameters of 3 μm, 1 μm, 0.3 μm and 0.05 μm, respectively, washing with distilled water, ultrasonic cleaning with absolute ethanol and distilled water, and air drying. Will 2mg PANI-Cu 2 O nano powder and 10 mu l of 5% Nafion ethanol solution are dispersed in 0.5ml of ethanol and are sonicated for 30min to form a uniform mixed suspension. And (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in 0.1M PBS (pH 6.8) for 2 hours under the condition of potential range of-0.1V to 0.9V (vs. SCE), and then constant potential scanning is carried out for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, the pretreated modified electrode was immersed in a 0.1M PBS solution for use.
Electrochemical testing employs a three-electrode system in which PANI-Cu is used 2 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, so as to carry out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. In order to obtain stable and high-sensitivity electrochemical signals, the modified electrode is subjected to constant potential scanning for 30 seconds under the condition of 0V before each DPV test, so that the modified electrode material is in an electrochemical reduction state. The entire test was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Comparative example
50mL of methylene chloride was added to the round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and dispersed uniformly by sonication to form a clear and homogeneous organic phase solution. The resulting organic phase solution was placed on a magnetic stirrer, 50mL of a 0.2mol/L aqueous solution of N-methylpyrrolidone 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 a round-bottom flask, after the standing reaction is carried out for 60 minutes, the lower dichloromethane layer is sucked out by a rubber head dropper and is 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.
The glassy carbon electrode with the diameter of 5mm is polished on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washed by distilled water, ultrasonically washed in absolute ethyl alcohol and distilled water respectively and then dried for standby. 2mg of PANI nanopowder 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 (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in 0.1M PBS (pH 6.8) for 2 hours under the condition of potential range of-0.1V to 0.9V (vs. SCE), and then constant potential scanning is carried out for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, the pretreated modified electrode was immersed in a 0.1M PBS solution for use.
The electrochemical test 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 for carrying out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. In order to obtain stable and high-sensitivity electrochemical signals, the modified electrode is subjected to constant potential scanning for 30 seconds under the condition of 0V before each DPV test, so that the modified electrode material is in an electrochemical reduction state. The entire test was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Test example:
FIG. 1 shows PANI and PANI-Cu 2 As can be seen from the SEM image of the O nano catalyst, the PANI nano carrier has a short fiber structure with the diameter of 30-60nm; cu (Cu) 2 O is a series of round particles with the diameter of 10-20nm and is uniformly distributed on the surface of the PANI nanofiber. PANI-Cu 2 Cu in O nano catalyst powder 2 The O loading was 10%.
FIG. 2 shows PANI-Cu 2 O nanocatalyst modified electrode in a solution containing 1mM UADPV test plot in 2mM AA, 200. Mu.M DA in 0.1M PBS (pH 6.8), the oxidation current potential of DA ranged from 0.06V to 0.4V, and the oxidation peak potential was 0.17V; the oxidation current potential of UA ranges from 0.24V to 0.4V, and the oxidation peak is 0.30V. Therefore, in the detection of the DA and UA coexistence system, the detection of DA is not interfered by the existence of UA; the UA concentration in the serum of healthy human body is 120-460 mu M, and the DA concentration is extremely low and is 0.01-1 mu M, so that the method provided by the invention is not interfered by DA when being used for detecting the UA concentration in the serum of human body.
FIG. 3 shows PANI and PANI-Cu 2 DPV test comparison of O nanocatalyst modified electrode in 0.1M PBS (pH 6.8) solution containing 200. Mu.M DA (A) and 1mM UA (B), as can be seen in FIG. 3A, DA in PANI-Cu 2 The oxidation peak potential on the O nano-catalyst modified electrode is slightly shifted negatively compared with the PANI, so that the anti-interference detection of DA and UA is facilitated; DA in PANI-Cu 2 The catalytic oxidation signal on the O nano-catalyst modified electrode is obviously enhanced compared with PANI. As can be seen from fig. 3B, UA is in PANI-Cu 2 Compared with PANI, the catalytic oxidation signal on the O modified electrode is enhanced to a certain extent, and the oxidation peak potential of the signal is not obviously shifted. Thus, cu is compounded 2 The PANI nano-catalyst modified electrode of O has obviously improved sensitivity and anti-interference detection on DA and UA.
FIG. 4 shows PANI-Cu 2 The DPV test chart of the O modified electrode in the 0.1M PBS (pH 6.8) solution containing DA with different concentrations shows that the oxidation current potential ranges of the DA with different concentrations on the modified electrode are all 0.06V-0.4V, and the oxidation peak potentials are all near 0.17V; as the concentration of DA increases, the electrochemical response signal of DA on the modified electrode increases, and the detection limit is 0.001. Mu.M. The concentration of DA in the extracellular fluid of healthy individuals is 0.01-1. Mu.M, while the concentration of DA in the extracellular fluid of Parkinson's patients is lower than 1nM. Therefore, the DA detection method provided by the invention has a sufficiently low detection limit, is hopeful to be used for detecting the DA content in extracellular fluid of a Parkinson patient, and is not interfered by UA.
FIG. 5 shows DA in PANI-Cu 2 Standard curve for DPV test on O-modified electrode,as can be seen from the graph, the concentration range detected in the present invention is 0.00. Mu.M-200. Mu.M, and the DA concentration and the peak current show a bilinear relationship. The linear curve at high concentration (5. Mu.M-200. Mu.M) is y=0.00613x+1.09548, the correlation coefficient R 2 = 0.99065. The linear curve at low concentration (0.001. Mu.M-5. Mu.M) is y=0.5018x+0.5135, the correlation coefficient R 2 ＝0.95652。
FIG. 6 is a PANI-Cu 2 The DPV test chart of the O modified electrode in the 0.1M PBS (pH 6.8) solution containing UA with different concentrations shows that the oxidation current potential ranges of UA with different concentrations on the modified electrode are all 0.24V-0.4V, and the oxidation peak potentials are all near 0.3V; as the UA concentration increases, the electrochemical response signal of UA on the modified electrode increases with the detection limit of 1 μm. Compared with the detection limit of camphorsulfonic acid doped PANI on UA 50 mu M, the detection limit of PANI-Cu 2 The detection limit of the O modified electrode to UA is obviously improved. The UA concentration in serum of healthy human body is 120-460 mu M, and the method provided by the invention has enough sensitivity to be used for detecting UA in serum of human body and is not interfered by DA in serum.
FIG. 7 shows UA in PANI-Cu 2 As can be seen from the graph, the UA test method provided by the invention has a wider linear detection concentration range of 1 mu M-1mM, the UA concentration and peak current show a linear relation, the linear curve is y=0.000607x+0.21267, and the correlation coefficient is R 2 ＝0.99108。
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the polyaniline-loaded cuprous oxide sensing electrode is characterized by comprising the following steps of:
s1: adding 0.5mL aniline monomer into 50mL methylene dichloride solution, and carrying out ultrasonic treatment to uniformly disperse the aniline monomer to form transparent uniform organic phase solution;
s2: sequentially adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g camphorsulfonic acid into the organic phase solution under the stirring condition, 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 in the step S2, standing for reaction for a preset time, separating the lower dichloromethane layer, and filtering the residual solution through a mixed system filter membrane to obtain a solid product;
s4: washing and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: dispersing 160mg camphorsulfonic acid doped PANI nano powder in 50ml glycol solution by ultrasonic, adding 0.25g pentahydrate copper sulfate and 0.04g PVP, stirring, dropwise adding 25ml of 0.09M sodium hydroxide aqueous solution, stirring, adding 25ml of 1.3M glucose aqueous solution after preset stirring time, stirring for a period of time, stirring under 80 ℃ condition for reaction 1-2h, filtering the product by a mixed filter membrane after the reaction is finished, washing the filtered solid product, and drying to obtain PANI-Cu 2 O nano powder;
s6: polishing the glassy carbon electrode on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use;
s7: PANI-Cu of 2mg 2 Adding O nano powder and 10 mu l of 5% Nafion ethanol solution into 0.5ml ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
s8: dripping 20 μl of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and air drying to obtain PANI-Cu 2 An O modified electrode;
further comprises the PANI-Cu to be prepared 2 The O modified electrode is subjected to cyclic voltammetry scanning for 2h under the condition of 0.1M PBS and the potential range of-0.1V to 0.9V, and then is subjected to constant potential scanning for 30min under the condition of 0V; repeating the operation for 3 times, and immersing the treated modified electrode in 0.1M PBS solution for standby;
s2, stirring for 20-30min at room temperature;
and (3) standing for 60-90min.
2. The preparation method of the polyaniline-loaded cuprous oxide sensing electrode according to claim 1, wherein the specific steps of S4 are as follows: washing the solid product with distilled water and ethanol in turn, cleaning the filtered product, and naturally airing to obtain camphorsulfonic acid doped PANI nano powder.
3. The preparation method of the polyaniline-loaded cuprous oxide sensing electrode according to the step 1, which is characterized in that the step S5 is added with copper sulfate pentahydrate and PVP and stirred for 30min; dropwise adding sodium hydroxide aqueous solution and stirring for 20-30min; adding glucose aqueous solution, and stirring for 20-30min.
4. The preparation method of the polyaniline-loaded cuprous oxide sensing electrode according to claim 1, wherein the specific steps of cleaning and drying the solid product in S5 are as follows: washing the solid product with absolute ethanol and pure water for 4-6 times, and naturally air drying to obtain PANI-Cu 2 O nanometer powder.
5. A polyaniline-loaded cuprous oxide sensing electrode, characterized in that the polyaniline-loaded cuprous oxide sensing electrode is produced by the method of any one of claims 2-4; the test environment is as follows: with PANI-Cu 2 The O modified electrode is a working electrode, the graphite electrode is a counter electrode, the saturated calomel electrode is a reference electrode, the pulse voltammetry test is carried out, the potential range of the pulse voltammetry test is-0.1V-0.9V, the scanning amplitude is 50mV, and the pulse width is 50ms.
6. The polyaniline loaded cuprous oxide sensing electrode as claimed in claim 5 wherein pulsed voltammetry is performed in 0.1M PBS solution at ph=6.8.
7. A polyaniline loaded cuprous oxide sensing electrode as claimed in claim 5 or 6 wherein the modified electrode is potentiostatic scanned at 0V for 30s prior to each pulsed voltammetry test.
CN202110991182.3A 2021-08-26 2021-08-26 Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof Active CN113804738B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110991182.3A CN113804738B (en) 2021-08-26 2021-08-26 Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110991182.3A CN113804738B (en) 2021-08-26 2021-08-26 Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof

Publications (2)

Publication Number Publication Date
CN113804738A CN113804738A (en) 2021-12-17
CN113804738B true CN113804738B (en) 2023-04-25

Family

ID=78941821

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110991182.3A Active CN113804738B (en) 2021-08-26 2021-08-26 Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof

Country Status (1)

Country Link
CN (1) CN113804738B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114985003B (en) * 2022-06-07 2023-11-17 西安理工大学 Preparation method and application of chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108130552A (en) * 2017-12-27 2018-06-08 东莞理工学院 A kind of polyaniline cuprous oxide composite material and its preparation method and application
CN108554449A (en) * 2018-06-04 2018-09-21 盐城师范学院 Application of a kind of quinoid structure compound in Visible Light Induced Photocatalytic methyl orange
CN108831760A (en) * 2018-06-15 2018-11-16 武汉工程大学 A kind of N doping MXene material and its preparation method and application
CN109239157A (en) * 2018-09-07 2019-01-18 常州大学 A kind of non-enzyme sensor of graphene-NiO- polyaniline
CN112750548A (en) * 2021-01-29 2021-05-04 厦门大学 Radioactive three-dimensional nanostructure photovoltaic electrochemical cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108130552A (en) * 2017-12-27 2018-06-08 东莞理工学院 A kind of polyaniline cuprous oxide composite material and its preparation method and application
CN108554449A (en) * 2018-06-04 2018-09-21 盐城师范学院 Application of a kind of quinoid structure compound in Visible Light Induced Photocatalytic methyl orange
CN108831760A (en) * 2018-06-15 2018-11-16 武汉工程大学 A kind of N doping MXene material and its preparation method and application
CN109239157A (en) * 2018-09-07 2019-01-18 常州大学 A kind of non-enzyme sensor of graphene-NiO- polyaniline
CN112750548A (en) * 2021-01-29 2021-05-04 厦门大学 Radioactive three-dimensional nanostructure photovoltaic electrochemical cell

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Andrews Nirmala Grace 等."Electrochemical reduction of carbon dioxide at low overpotential on a polyaniline/Cu2O nanocomposite based electrode".《Applied Energy》.2014,(第120期),85-94. *
K.Gopalakrishnan 等."Optical and Magnetic Studies on Cu2O/PANI Nanocomposite Prepared by Chemical Polymerization Method".《ISRN Materials Science》.2014,(第2014期),1-8. *

Also Published As

Publication number Publication date
CN113804738A (en) 2021-12-17

Similar Documents

Publication Publication Date Title
Hira et al. Ultrasensitive detection of hydrogen peroxide and dopamine using copolymer-grafted metal-organic framework based electrochemical sensor
CN110514728B (en) High-sensitivity Fe-PANI/Pt @ Au dopamine electrochemical detection electrode and preparation thereof
CN113406171B (en) Composite electrode and preparation method and application thereof
CN113813945B (en) Three-dimensional space network graphene-based polyaniline/PtAg composite catalyst and preparation method thereof
CN103175884A (en) High-sensitivity glucose biosensor and preparation method thereof
CN111537589A (en) Method for detecting glucose based on cobalt-based metal organic framework enzyme-free glucose sensor
CN113804738B (en) Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof
JP6684381B1 (en) Method for detecting trace carbadox using direct electrochemical sensor with mesoporous carbon CMK-8 having cubic Ia3d structure
CN113916959B (en) Pt-Au catalyst loaded by porous polyaniline/graphene-based composite microspheres
CN110441360A (en) A kind of preparation method of one-dimensional copper nano-wire glucose sensor electrode material
CN105911128B (en) A kind of enzyme-free glucose electrochemical sensor and its application
CN110514725B (en) Fe-PANI-based dopamine electrochemical sensing electrode and preparation thereof
CN110514726B (en) Fe-PANI/Au modified electrode for sensitive detection of dopamine and uric acid and preparation thereof
CN113267544A (en) Method for monitoring hydrogen peroxide concentration in living cell based on three-dimensional sensing and electrode
CN110514727B (en) Iron-doped polyaniline/platinum-based dopamine selective electrochemical detection electrode and preparation thereof
CN113884560B (en) Graphene-based Pt-Pd bimetallic nanocomposite and preparation method thereof
Huang et al. Functionalized Graphene Fiber Modified With MOF-Derived Rime-Like Hierarchical Nanozyme for Electrochemical Biosensing of H2O2 in Cancer Cells
CN114965629B (en) Lactic acid biosensor and preparation method thereof, and cell viability electrochemical detection method
CN113804737B (en) Polyaniline loaded silver/cuprous oxide multi-element nanocomposite and preparation method of modified electrode
CN114371201B (en) Reusable glucose sensor and preparation method and application thereof
CN101963593A (en) Beta-CD-SBA15 modified electrode and method for measuring nitrophenol isomerides
CN109487370A (en) MOF-235-500 DEG C of material of spinning and its preparation method and application
CN116087288A (en) 3D-rGO-Fe 3 O 4 CS-SA compound modified electrode and preparation method and application thereof
CN114527185A (en) Copper-silver-loaded few-layer graphene-based composite material and preparation method and application thereof
CN113916960B (en) Space-limited polyaniline@graphene/Ag nanocomposite

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