CN110887882B - Enzyme-free glucose sensor and preparation method thereof - Google Patents
Enzyme-free glucose sensor and preparation method thereof Download PDFInfo
- Publication number
- CN110887882B CN110887882B CN201911232624.5A CN201911232624A CN110887882B CN 110887882 B CN110887882 B CN 110887882B CN 201911232624 A CN201911232624 A CN 201911232624A CN 110887882 B CN110887882 B CN 110887882B
- Authority
- CN
- China
- Prior art keywords
- sodium
- tetrafluorocuprate
- composite material
- carbon material
- nanoparticle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an enzyme-free glucose sensor and a preparation method thereof, wherein sodium tetrafluorocuprate nanoparticles and a carbon material are adopted to prepare a sodium tetrafluorocuprate nanoparticle-carbon material composite material; and modifying the noble metal electrode by using the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material to obtain the enzyme-free glucose sensor. The enzyme-free glucose sensor has high electrocatalytic activity, strong anti-interference performance, good stability, simple preparation method and low cost, and is beneficial to mass preparation.
Description
Technical Field
The invention relates to the technical field of chemical synthesis and biomedical engineering, in particular to a preparation method of an enzyme-free glucose sensor based on a composite material of sodium tetrafluorocuprate and a carbon material.
Background
The concentration of glucose is one of the important indicators for the diagnosis and treatment of diabetes. Therefore, the accurate and rapid glucose measurement is of great significance. At present, glucose sensors are mainly enzyme type glucose sensors. Although the enzyme type glucose sensor has the advantages of good selectivity and high sensitivity. However, enzymes of the enzymatic glucose sensor are susceptible to environmental influences and lose activity, thereby causing instability of the sensor. In addition, the immobilization of the enzyme is difficult, resulting in poor reproducibility of the enzyme-type glucose sensor. The non-enzymatic glucose sensor does not depend on the activity of biomolecules, so the non-enzymatic glucose sensor has the advantages of good stability, good repeatability and simple structure.
At present, a gold electrode modified with a gold-graphene oxide nanocomposite for non-enzymatic sensing of glucose at near-neutral pH values, which is a non-enzymatic glucose sensor prepared based on gold nano-materials, is widely applied to the development of enzyme-free glucose sensors.
Chinese invention patent application no: 201710682831.5, discloses a preparation method of an enzyme-free glucose sensor, which comprises an electrode modification materialPreparing the modified electrode; the used modification materials mainly comprise reductive graphene RGO and nano magnetic iron oxide Fe2O3Graphene iron oxide RGO-Fe combined with chitosan CS2O3Nanocomposites, and platinum nanoparticles PtNps. Also, such sensors are expensive to manufacture and not conducive to large scale manufacturing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an enzyme-free glucose sensor, which improves the electrocatalytic activity, anti-interference performance and stability of the glucose sensor, is simple and convenient to prepare, has low cost and is beneficial to mass preparation.
In order to achieve the above object, the present invention provides a method for preparing an enzyme-free glucose sensor, comprising:
preparing a sodium tetrafluorocuprate nanoparticle-carbon material composite material by adopting sodium tetrafluorocuprate nanoparticles and a carbon material;
and modifying the noble metal electrode by using the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material to obtain the enzyme-free glucose sensor.
Optionally, the sodium tetrafluorocuprate nanoparticles are prepared by the following method:
adding copper chloride and hydrofluoric acid into a container, and stirring to obtain a sodium tetrafluorocuprate acid solution;
slowly adding a sodium hydroxide solution into the acid solution of the sodium tetrafluorocuprate and stirring to obtain a sodium tetrafluorocuprate precipitate;
and (4) centrifugally washing and drying to obtain the sodium tetrafluorocuprate nanoparticles.
The preparation method of the preferable sodium tetrafluorocuprate nano-particles has the advantages of simpler manufacturing process, simpler equipment and lower cost, can control the appearance of the generated sodium tetrafluorocuprate nano-particles, and has a catalytic effect on glucose.
Optionally, the method comprises the following steps: the molecular number of the measured hydrofluoric acid is more than or equal to twice of the molecular number of the weighed copper chloride.
Optionally, the carbon material comprises any one or more of carbon nanotubes, carbon nanohorns, graphite, graphene, carbon fibers, carbon spheres, carbon aerogel and graphdiyne, and the selected carbon material can effectively enhance the conductivity of the sodium tetrafluorocuprate nanoparticle composite material, so as to enhance the catalytic activity of the composite material.
Alternatively, the material of the noble metal electrode may be: gold, platinum, palladium, or alloys thereof, the noble metal electrode material selected being of the class of noble metal materials commonly used as electrodes.
Alternatively, the noble metal electrode means any one of noble metal wires, rods, and sheets, and the selected electrode shape is a noble metal shape type commonly used as an electrode.
Optionally, the fixing of the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material to the surface of the noble metal electrode comprises:
preparing the sodium tetrafluorocuprate nano particles or the sodium tetrafluorocuprate nano particle-carbon material composite material into a dispersion liquid and then dropwise adding the dispersion liquid; or, preparing the sodium tetrafluorocuprate nano-particles or the sodium tetrafluorocuprate nano-particles-carbon material composite material into electroplating solution and then carrying out electrodeposition; or dispersing the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material into gel for coating;
the surface of the electrode is covered by the sodium tetrafluorocuprate nano-particles or the sodium tetrafluorocuprate nano-particle-carbon material composite material through the dropping, the electro-deposition or the coating. The method of fixing the material selected is all the commonly used method of fixing the electrode material to the electrode.
Optionally, the dropping after the dispersion is prepared refers to: and dropwise adding the dispersion liquid of the material to the surface of the electrode, drying, and repeating the steps for a plurality of times until the surface of the electrode is covered by the composite material, wherein the selected dispersion liquid dropwise adding method can effectively ensure the combination of the sodium tetrafluorocuprate-based material and the noble metal electrode.
Alternatively, the dispersion is: the material is dispersed in any one of water, organic solvents such as ethanol, acetone and the like and mixtures thereof in any proportion to prepare a dispersion liquid, and the preparation method of the dispersion liquid is all the methods which are commonly used for dispersing solid materials into liquid.
Alternatively, the electrodeposition after the plating solution is prepared refers to: the material is prepared into electroplating solution with any concentration and then is fixed on the noble metal electrode through electrodeposition, and the selected electroplating mode can ensure that a more uniform and stable plating layer is obtained.
Alternatively, the dispersion into the gel is coated, which means that: the material is dispersed into any one of gels such as Nafion, chitosan and the like and mixtures thereof in any proportion to be coated on the noble metal electrode, and the material can be ensured to be uniformly and stably coated on the surface of the electrode by the selected method of dispersing into the gel and coating.
Optionally, said covering by material means: the thickness of the material fixed on the noble metal electrode by the method is 10 nanometers to 100 micrometers, and the thickness of the material layer is selected to be suitable for the noble metal electrode with the whole shape and obtain stable catalytic effect.
Optionally, the taking of the copper chloride and the hydrofluoric acid means that the number of molecules of the measured hydrofluoric acid is greater than or equal to two times of the number of molecules of the measured copper chloride, and the ratio of the copper chloride to the hydrofluoric acid is selected to ensure that the hydrofluoric acid is sufficient to avoid the generation of copper hydroxide precipitate during the adding of the sodium hydroxide solution.
The invention also provides the enzyme-free glucose sensor obtained by the preparation method of the enzyme-free glucose sensor.
Compared with the prior art, the invention has at least one of the following beneficial effects:
most of the existing sensors for detecting glucose without enzyme are made of composite material modified glassy carbon electrodes, and the testing method is only related to the catalytic activity of the prepared material. According to the enzyme-free glucose sensor and the preparation method thereof, the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material is adopted for precious metal electrode modification, and the transition metal base material and the surface of the gold electrode have a synergistic effect, so that the catalytic activity is improved.
According to the enzyme-free glucose sensor and the preparation method thereof, the sodium tetrafluorocuprate nano particles and the sodium tetrafluorocuprate nano particles-carbon material composite material prepared by the optimal method are adopted, the cost of the preparation method is greatly reduced, and the shape of the material is controllable. Although the existing method has higher purity, the process is more complicated and the cost is higher, and the sodium tetrafluorocuprate prepared by the method has higher glucose catalytic activity.
The enzyme-free glucose sensor and the preparation method thereof improve the electrocatalytic activity, anti-interference performance and stability of glucose, have simple and convenient preparation process and low cost, and are beneficial to mass preparation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram illustrating the steps of a method for making an enzyme-free glucose sensor according to one embodiment of the invention;
FIG. 2 is a schematic diagram of the structure of a non-enzymatic glucose sensor in accordance with one embodiment of the invention;
in the figure: sodium tetrafluorocuprate nanoparticles or sodium tetrafluorocuprate nanoparticles-carbon material composite material 1, noble metal electrode 2;
FIG. 3 is a schematic diagram illustrating the steps of a method for manufacturing an enzyme-free glucose sensor according to a first embodiment of the present invention;
FIG. 4 is a schematic diagram illustrating the steps of a method for manufacturing an enzyme-free glucose sensor according to a second embodiment of the present invention;
FIG. 5 is a schematic diagram illustrating the steps of a method for manufacturing an enzyme-free glucose sensor according to a third embodiment of the present invention;
FIG. 6 is a schematic diagram illustrating the steps of a method for manufacturing an enzyme-free glucose sensor according to a fourth embodiment of the present invention;
fig. 7 is a graph showing the result of the experiment of the first embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
FIG. 1 is a schematic diagram illustrating the steps of a method for manufacturing an enzyme-free glucose sensor according to an embodiment of the present invention; the preparation method of the enzyme-free glucose sensor shown in the figure is a method for obtaining the enzyme-free glucose sensor by modifying a noble metal electrode with a sodium tetrafluorocuprate nanoparticle-carbon material composite material.
As shown in fig. 2, which is a schematic structural diagram of the enzyme-free glucose sensor obtained in an embodiment of the present invention, the sensor structure includes sodium tetrafluorocuprate nanoparticles or sodium tetrafluorocuprate nanoparticles-carbon material composite material 1 and a noble metal electrode 2, the sodium tetrafluorocuprate nanoparticles or sodium tetrafluorocuprate nanoparticles-carbon material composite material 1 is fixed on the surface of the noble metal electrode 2, and uniformly covers the surface of the noble metal electrode 2, and the thickness of the material fixed on the noble metal electrode is 10 nm to 100 μm.
Referring to fig. 3, a method for preparing an enzyme-free glucose sensor based on sodium tetrafluorocuprate nanoparticles according to a first embodiment of the present invention includes:
s101, weighing copper chloride, measuring hydrofluoric acid with the mass fraction of 40%, adding the copper chloride into a container, and stirring to obtain the sodium tetrafluorocuprate acid solution.
Specifically, 1g of copper chloride, 20ml of hydrofluoric acid with the mass fraction of 40% is taken, the molecular number of the hydrofluoric acid is more than or equal to twice that of the copper chloride, the hydrofluoric acid is added into a plastic container, tetrafluoroethylene magnetons are used for magnetic stirring to obtain a sodium tetrafluoro cuprate acidic solution, the tetrafluoroethylene magnetons are used for magnetic stirring, the solution can be fully mixed and does not splash liquid, the selected stirring mode can ensure that the reaction is fully performed and the personnel safety is ensured, and the selected weighing and measuring mode can accurately ensure the content of each component in the preparation process.
S102, slowly adding 0.1 mol/L sodium hydroxide solution into the acid solution of the sodium tetrafluorocuprate, and stirring to obtain the sodium tetrafluorocuprate precipitate.
Specifically, a sodium hydroxide solution with the concentration of 0.1 mol/L is slowly added into the acid sodium tetrafluorocuprate solution, and the pH is adjusted to be neutral by stirring at a constant speed, so that a white solid precipitate of the sodium tetrafluorocuprate is formed in the mixed solution, the purpose of slowly adding the sodium hydroxide solution is to ensure that the temperature of the mixed solution is not obviously increased after the sodium hydroxide solution is added, the temperature of the reaction system is kept at normal temperature, and the mixed solution is prevented from being alkaline due to excessive sodium hydroxide, so that a copper hydroxide precipitate is generated.
S103, centrifuging, washing and drying to obtain the sodium tetrafluorocuprate nanoparticles.
Specifically, the mixed solution of the white solid precipitate containing the sodium tetrafluorocuprate is centrifuged at 12000 r/min for 15 min for more than or equal to 20 times, and is dried in vacuum to obtain pure sodium tetrafluorocuprate nanoparticles, so that the soluble substances except the sodium tetrafluorocuprate precipitate can be effectively removed.
And S104, dispersing the sodium tetrafluorocuprate nano particles into deionized water, dropwise adding the sodium tetrafluorocuprate nano particles to the surface of the gold sheet, and naturally drying to form the modified gold electrode.
Specifically, 1g of sodium tetrafluorocuprate nanoparticles is mixed with 10ml of deionized water, a cell disruptor is used for carrying out ultrasound for 30 minutes under the conditions that the power is 100W, the ultrasound lasts for 2 seconds and stops for 1 second, uniform and stable dispersion liquid can be formed on the premise that the microstructure of the material is not damaged, a small amount of sodium tetrafluorocuprate nanoparticle dispersion liquid is dripped on the surface of a cleaned gold sheet and is placed in a dust-free environment to be dried at natural temperature, the combination of the sodium tetrafluorocuprate nanoparticles and the gold sheet can be effectively guaranteed, and the sodium tetrafluorocuprate nanoparticle modified gold electrode is obtained.
The cleaned gold flakes are obtained by sequentially using acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaning machine, respectively ultrasonically cleaning for 3 minutes and drying under nitrogen flow; the cleaning can effectively remove stains on the surface of the gold sheet so as to ensure the purity of the sodium tetrafluorocuprate nanoparticles dried on the gold sheet, the relative surface area of the prepared sodium tetrafluorocuprate nanoparticle modified gold electrode is obviously increased, and the sodium tetrafluorocuprate nanoparticle modified gold electrode can be obtained through anti-interference test, stability test and glucose detection, has good anti-interference performance and high stability, obviously improves the catalytic activity on glucose, and can effectively resist the interference of various interference substances such as lactose, galactose, lactic acid, dopamine, sucrose, ascorbic acid and the like in human body fluid.
Referring to fig. 4, a second embodiment of the present invention provides a method for preparing an enzyme-free glucose sensor based on a sodium tetrafluorocuprate nanoparticle-multiwalled carbon nanotube composite material, including:
s201, weighing copper chloride, measuring hydrofluoric acid with the mass fraction of 40%, and adding the copper chloride and the hydrofluoric acid into a plastic container to stir to obtain the acid solution of the sodium tetrafluorocuprate.
Specifically, 1g of copper chloride is weighed by an electronic balance or a weight balance, 20ml of hydrofluoric acid with the mass fraction of 40% is measured by a plastic measuring cylinder or a pipette, the number of molecules of the hydrofluoric acid is more than or equal to twice that of the copper chloride molecules, the hydrofluoric acid is added into a plastic container, magnetic stirring is carried out by using a tetrafluoroethylene magneton to obtain a sodium tetrafluorocuprate acid solution, and the magnetic stirring is carried out by using the tetrafluoroethylene magneton to enable the solution to be fully mixed and not to splash liquid.
S202, slowly adding 0.1 mol/L sodium hydroxide solution into the acid solution of the sodium tetrafluorocuprate, and stirring to obtain the sodium tetrafluorocuprate precipitate.
Specifically, a sodium hydroxide solution with the concentration of 0.1 mol/L is slowly added into the acid sodium tetrafluorocuprate solution, and the pH is adjusted to be neutral by stirring at a constant speed, so that a white solid precipitate of the sodium tetrafluorocuprate is formed in the mixed solution, the purpose of slowly adding the sodium hydroxide solution is to ensure that the temperature of the mixed solution is not obviously increased after the sodium hydroxide solution is added, the temperature of the reaction system is kept at normal temperature, and the mixed solution is prevented from being alkaline due to excessive sodium hydroxide, so that a copper hydroxide precipitate is generated.
S203, washing and drying through centrifugation to obtain the sodium tetrafluorocuprate nano particles.
Specifically, the mixed solution of the white solid precipitate containing the sodium tetrafluorocuprate is centrifuged at 12000 r/min for 15 min for more than or equal to 20 times, and is dried in vacuum to obtain pure sodium tetrafluorocuprate nanoparticles, so that the soluble substances except the sodium tetrafluorocuprate precipitate can be effectively removed.
S204, weighing the sodium tetrafluorocuprate nanoparticles and the multi-walled carbon nanotubes, adding the sodium tetrafluorocuprate nanoparticles and the multi-walled carbon nanotubes into deionized water, and obtaining the sodium tetrafluorocuprate nanoparticle-multi-walled carbon nanotube composite material in an ultrasonic mode.
Specifically, 1g of sodium tetrafluorocuprate nanoparticles and 0.5g of multiwall carbon nanotubes are weighed and added into deionized water, the mass of the sodium tetrafluorocuprate nanoparticles is twice that of the multiwall carbon nanotubes, and a cell disruptor is used for carrying out ultrasonic treatment for 2 hours under the conditions of 800W power and ultrasonic treatment for 2 seconds to stop for 1 second, so that the sodium tetrafluorocuprate nanoparticle-multiwall carbon nanotube composite material is obtained, wherein the mass ratio of the selected sodium tetrafluorocuprate nanoparticles to the multiwall carbon nanotubes can effectively ensure that the sodium tetrafluorocuprate and the multiwall carbon nanotubes are uniformly mixed, the catalytic activity of the composite material is enhanced, and the selected multiwall carbon nanotubes can effectively enhance the conductivity of the sodium tetrafluorocuprate nanoparticle composite material, so that the catalytic activity of the composite material is enhanced.
S205, dispersing the sodium tetrafluorocuprate nanoparticle-multi-walled carbon nanotube composite material into deionized water, dropwise adding the composite material to the surface of a gold wire, and naturally drying to form the modified gold electrode.
Specifically, the gold wire is respectively ultrasonically cleaned for 3 minutes by acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaning machine, and is dried under nitrogen flow, the dispersed liquid of the sodium tetrafluorocuprate nanoparticle-multiwalled carbon nanotube composite material is dripped on the surface of the cleaned gold wire, the gold wire is placed in a dust-free environment and is dried at natural temperature to form the sodium tetrafluorocuprate nanoparticle-multiwalled carbon nanotube composite material modified gold electrode, the cleaning method can effectively remove stains on the surface of the gold wire so as to ensure the purity of the sodium tetrafluorocuprate nanoparticle-multiwalled carbon nanotube composite material dried on the gold wire, the relative surface area of the prepared sodium tetrafluorocuprate nanoparticle-multiwalled carbon nanotube composite material modified gold electrode is obviously increased, and the modified gold electrode can be obtained through anti-interference tests, stability tests and glucose tests, the sodium tetrafluorocuprate nanoparticle-multiwalled carbon nanotube composite material modified gold electrode has good anti-interference performance and high stability, and the catalytic activity on glucose is obviously improved.
Referring to fig. 5, a third embodiment of the present invention provides a method for preparing an enzyme-free glucose sensor based on a sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material, comprising:
s301, weighing copper chloride, measuring hydrofluoric acid with the mass fraction of 40%, and adding the copper chloride and the hydrofluoric acid into a plastic container to stir to obtain the sodium tetrafluorocuprate acid solution.
Specifically, use electronic balance or weight balance to weigh 1g copper chloride, and measure 20ml mass fraction for 40% hydrofluoric acid with plastics graduated flask or pipettor, the molecule number of hydrofluoric acid is more than or equal to the twice of copper chloride molecule number, and add in the plastic container, use the tetrafluoroethylene magneton to carry out magnetic stirring, obtain tetrafluoro cuprate acid sodium acid solution, use the tetrafluoroethylene magneton to carry out magnetic stirring, can make the solution can the intensive mixing and liquid splash, the stirring mode of selecting can guarantee that the reaction fully goes on and guarantee experimenter safety, and the content of each component in the preparation process can be guaranteed accurately to the mode of selecting weighing and measuring.
S302, slowly adding 0.1 mol/L sodium hydroxide solution into the acid solution of the sodium tetrafluorocuprate, and stirring to obtain the sodium tetrafluorocuprate precipitate.
Specifically, a sodium hydroxide solution with the concentration of 0.1 mol/L is slowly added into the acid sodium tetrafluorocuprate solution, and the pH is adjusted to be neutral by stirring at a constant speed, so that a white solid precipitate of the sodium tetrafluorocuprate is formed in the mixed solution, the purpose of slowly adding the sodium hydroxide solution is to ensure that the temperature of the mixed solution is not obviously increased after the sodium hydroxide solution is added, the temperature of the reaction system is kept at normal temperature, and the mixed solution is prevented from being alkaline due to excessive sodium hydroxide, so that a copper hydroxide precipitate is generated.
S303, centrifuging, washing and drying to obtain the sodium tetrafluorocuprate nano particles.
Specifically, the mixed solution of the white solid precipitate containing the sodium tetrafluorocuprate is centrifuged at 12000 r/min for 15 min for more than or equal to 20 times, and is dried in vacuum to obtain pure sodium tetrafluorocuprate nanoparticles, so that the soluble substances except the sodium tetrafluorocuprate precipitate can be effectively removed.
S304, weighing the sodium tetrafluorocuprate nanoparticles and the single-walled carbon nanohorns, adding the sodium tetrafluorocuprate nanoparticles and the single-walled carbon nanohorns into deionized water, and obtaining the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material in an ultrasonic mode.
Specifically, 1g of sodium tetrafluorocuprate nanoparticles and 0.5g of single-walled carbon nanohorns are weighed and added into deionized water, the mass of the sodium tetrafluorocuprate nanoparticles is twice that of the single-walled carbon nanohorns, and a cell crusher is used for carrying out ultrasonic treatment for 2 hours under the conditions of 800W power and 2-second ultrasonic stop for 1 second to obtain the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material, wherein the mass ratio of the selected sodium tetrafluorocuprate nanoparticles to the single-walled carbon nanohorns can effectively ensure the uniform mixing of the sodium tetrafluorocuprate and the single-walled carbon nanohorns, so that the catalytic activity of the composite material is enhanced, and the selected single-walled carbon nanohorns can effectively enhance the electrical conductivity of the sodium tetrafluorocuprate nanoparticle composite material, so that the catalytic activity of the composite material is enhanced.
S305, dispersing the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material into deionized water to prepare electroplating solution, electroplating a platinum sheet serving as an electrode to be electroplated, and electroplating for a period of time to form a modified platinum electrode.
Specifically, a platinum sheet is respectively ultrasonically cleaned for 3 minutes by acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaning machine, and is dried under nitrogen flow, the platinum sheet and a counter electrode are immersed into dispersion liquid of the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material, the dispersion liquid is respectively connected with a positive electrode and a negative electrode of a power supply, the constant voltage mode is used for electroplating, the set voltage is 0.5 volt, the deposition time is 3000 seconds, the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material modified platinum electrode is formed, the cleaning method can effectively remove stains on the surface of the platinum sheet, so that the purity of the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material dried on the platinum sheet is ensured, the relative surface area of the prepared sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material modified platinum electrode is remarkably increased, the anti-interference performance test is carried out, and the anti-interference property, Stability test and glucose detection can show that the sodium tetrafluorocuprate nanoparticle-single-walled carbon nanohorn composite material modified platinum electrode has good anti-interference performance, high stability and obviously improved catalytic activity on glucose.
Referring to fig. 6, a fourth embodiment of the present invention provides a method for preparing an enzyme-free glucose sensor based on a sodium tetrafluorocuprate nanoparticle-graphene composite material, including:
s401, weighing copper chloride, measuring hydrofluoric acid with the mass fraction of 40%, adding the copper chloride into a plastic container, and stirring to obtain the sodium tetrafluorocuprate acid solution.
Specifically, use electronic balance or weight balance to weigh 1g copper chloride, and measure 20ml mass fraction for 40% hydrofluoric acid with plastics graduated flask or pipettor, the molecule number of hydrofluoric acid is more than or equal to the twice of copper chloride molecule number, and add in the plastic container, use the tetrafluoroethylene magneton to carry out magnetic stirring, obtain tetrafluoro cuprate acid sodium acid solution, use the tetrafluoroethylene magneton to carry out magnetic stirring, can make the solution can the intensive mixing and liquid splash, the stirring mode of selecting can guarantee that the reaction fully goes on and guarantee experimenter safety, and the content of each component in the preparation process can be guaranteed accurately to the mode of selecting weighing and measuring.
S402, slowly adding 0.1 mol/L sodium hydroxide solution into the acid solution of the sodium tetrafluorocuprate, and stirring to obtain the sodium tetrafluorocuprate precipitate.
Specifically, a sodium hydroxide solution with the concentration of 0.1 mol/L is slowly added into the acid sodium tetrafluorocuprate solution, and the pH is adjusted to be neutral by stirring at a constant speed, so that a white solid precipitate of the sodium tetrafluorocuprate is formed in the mixed solution, the purpose of slowly adding the sodium hydroxide solution is to ensure that the temperature of the mixed solution is not obviously increased after the sodium hydroxide solution is added, the temperature of the reaction system is kept at normal temperature, and the mixed solution is prevented from being alkaline due to excessive sodium hydroxide, so that a copper hydroxide precipitate is generated.
And S403, centrifugally washing and drying to obtain the sodium tetrafluorocuprate nanoparticles.
Specifically, the mixed solution of the white solid precipitate containing the sodium tetrafluorocuprate is centrifuged at 12000 r/min for 15 min for more than or equal to 20 times, and is dried in vacuum to obtain pure sodium tetrafluorocuprate nanoparticles, so that the soluble substances except the sodium tetrafluorocuprate precipitate can be effectively removed.
S404, weighing the sodium tetrafluorocuprate nanoparticles and the graphene, adding the sodium tetrafluorocuprate nanoparticles and the graphene into deionized water, and obtaining the sodium tetrafluorocuprate nanoparticle-graphene composite material in an ultrasonic mode.
Specifically, 1g of sodium tetrafluorocuprate nanoparticles and 0.5g of graphene are weighed and added into deionized water, the mass of the sodium tetrafluorocuprate nanoparticles is twice that of the graphene, a cell disruptor is used for carrying out ultrasound for 2 hours under the conditions of 800W power and ultrasound stop for 2 seconds to obtain the sodium tetrafluorocuprate nanoparticle-graphene composite material, wherein the mass ratio of the selected sodium tetrafluorocuprate nanoparticles to the graphene can effectively ensure the uniform mixing of the sodium tetrafluorocuprate and the graphene, the catalytic activity of the composite material is further enhanced, the selected graphene can effectively enhance the conductivity of the sodium tetrafluorocuprate nanoparticle composite material, and the catalytic activity of the composite material is further enhanced.
S405, dispersing the sodium tetrafluorocuprate nanoparticle-graphene composite material into chitosan, coating the chitosan on the surface of a platinum sheet, and naturally drying to form the modified platinum electrode.
Specifically, a platinum sheet is respectively ultrasonically cleaned for 3 minutes in an ultrasonic cleaning machine by using acetone, absolute ethyl alcohol and deionized water in sequence, and is dried under nitrogen flow, the sodium tetrafluorocuprate nanoparticle-graphene composite material is dispersed into chitosan, the chitosan is coated on the surface of the cleaned platinum sheet, the platinum sheet is placed in a dust-free environment and is dried at natural temperature to form the sodium tetrafluorocuprate nanoparticle-graphene composite material modified platinum electrode High stability and obviously improved catalytic activity to glucose.
The sodium tetrafluorocuprate nanoparticle modified gold electrode prepared in the embodiment has a remarkably increased relative surface area, and can be obtained through an anti-interference test, a stability test and a glucose test, the sodium tetrafluorocuprate nanoparticle modified gold electrode has good anti-interference performance and high stability, the catalytic activity on glucose is remarkably improved, and the interference of various interference substances in human body fluid such as lactose, galactose, lactic acid, dopamine, sucrose, ascorbic acid and the like can be effectively resisted, through the test, as shown in fig. 7, the obtained glucose sensor has three linear ranges of a first linear range (0.01-0.15mM), a second linear range (0.15-19.15mM) and a third linear range (19.15-63.15mM), and the sensitivity of the three linear ranges is 229.68 muA mM respectively-1cm-2、62.8μA mM-1cm-2、235.54μA mM-1cm-2. The sodium tetrafluorocuprate nano-particles or the sodium tetrafluorocuprate nano-particles-carbon material composite material modified noble metal electrode obtained in the embodiment has the advantages of improving the electrocatalytic activity, anti-interference performance and stability of glucose, being simple and convenient to operate and low in manufacturing cost, and being beneficial to mass preparation.
It should be understood that the foregoing is only a partial embodiment, and the specific parameter values in the foregoing embodiment are for better illustrating the method of the present invention, and are not limited to the parameter values, and it is obvious to those skilled in the art that in other embodiments, other values may be selected according to the practical application. The above preferred features can be used alone in any embodiment, or in any combination thereof, without conflict. It will be understood by those skilled in the art that all or a portion of the above-described embodiments may be practiced and equivalents thereof may be resorted to as falling within the scope of the invention as claimed.
Claims (10)
1. A method of making an enzyme-free glucose sensor, comprising:
modifying the noble metal electrode with the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material to obtain the enzyme-free glucose sensor, wherein:
the sodium tetrafluorocuprate nanoparticle-carbon material composite material is prepared from sodium tetrafluorocuprate nanoparticles and a carbon material.
2. The method of claim 1, wherein the sodium tetrafluorocuprate nanoparticle-carbon material composite is prepared from sodium tetrafluorocuprate nanoparticles and a carbon material, and comprises:
and adding the sodium tetrafluorocuprate nanoparticles and the carbon material into deionized water, obtaining the sodium tetrafluorocuprate nanoparticle-carbon material composite material in an ultrasonic mode, and centrifugally washing and drying to obtain the sodium tetrafluorocuprate nanoparticle-carbon material composite material.
3. The method of claim 1, wherein the modified noble metal electrode comprises:
and fixing the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material on the surface of a noble metal electrode to form the noble metal electrode modified by the sodium tetrafluorocuprate nanoparticle-carbon material composite material.
4. The method of claim 3, wherein the immobilizing sodium tetrafluorocuprate nanoparticles or sodium tetrafluorocuprate nanoparticle-carbon material composite material to the surface of the noble metal electrode comprises:
preparing the sodium tetrafluorocuprate nano particles or the sodium tetrafluorocuprate nano particle-carbon material composite material into a dispersion liquid and then dropwise adding the dispersion liquid; or, preparing the sodium tetrafluorocuprate nano-particles or the sodium tetrafluorocuprate nano-particles-carbon material composite material into electroplating solution and then carrying out electrodeposition; or dispersing the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material into gel for coating;
the surface of the electrode is covered by the sodium tetrafluorocuprate nano-particles or the sodium tetrafluorocuprate nano-particle-carbon material composite material through the dropping, the electro-deposition or the coating.
5. The method of claim 4 for preparing an enzyme-free glucose sensor, wherein:
the dropping after the dispersion liquid is prepared refers to: dripping the dispersion liquid of the sodium tetrafluorocuprate nano particles or the sodium tetrafluorocuprate nano particles-carbon material composite material onto the surface of the electrode, drying, and repeating the steps for a plurality of times until the surface of the electrode is covered by the composite material;
the electrodeposition after the electroplating solution is prepared refers to: preparing the sodium tetrafluorocuprate nano particles or the sodium tetrafluorocuprate nano particles-carbon material composite material into electroplating solution at any concentration, and then fixing the electroplating solution on a noble metal electrode through electrodeposition;
the dispersion is coated in gel, and means that: and dispersing the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material into gel or a gel mixture in any proportion, and then coating the gel or the gel mixture on a noble metal electrode.
6. The method of claim 4 for preparing an enzyme-free glucose sensor, wherein: the coated carbon material is coated with sodium tetrafluorocuprate nanoparticles or sodium tetrafluorocuprate nanoparticle-carbon material composite materials, wherein: the thickness of the sodium tetrafluorocuprate nanoparticles or the sodium tetrafluorocuprate nanoparticle-carbon material composite material fixed on the noble metal electrode is 10 nanometers to 100 micrometers.
7. The method of claim 1, wherein the sodium tetrafluorocuprate nanoparticles are prepared by:
adding copper chloride and hydrofluoric acid into a container, and stirring to obtain a sodium tetrafluorocuprate acid solution;
slowly adding a sodium hydroxide solution into the acid solution of the sodium tetrafluorocuprate and stirring to obtain a sodium tetrafluorocuprate precipitate;
and (4) centrifugally washing and drying to obtain the sodium tetrafluorocuprate nanoparticles.
8. The method of claim 7, wherein the copper chloride and hydrofluoric acid are taken, and wherein: the molecular number of the measured hydrofluoric acid is more than or equal to twice of the molecular number of the weighed copper chloride.
9. The method of any one of claims 1-8 for preparing an enzyme-free glucose sensor, further comprising one or more of the following:
-the carbon material comprises any one or more of carbon nanotubes, carbon nanohorns, graphite, graphene, carbon fibers, carbon spheres, carbon aerogel, graphdiyne;
the material of the noble metal electrode is any one or more of gold, platinum and palladium;
the noble metal electrode is any one of a noble metal wire, a rod and a sheet.
10. An enzyme-free glucose sensor, obtainable by the method of any one of claims 1 to 9 for the preparation of an enzyme-free glucose sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232624.5A CN110887882B (en) | 2019-12-05 | 2019-12-05 | Enzyme-free glucose sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232624.5A CN110887882B (en) | 2019-12-05 | 2019-12-05 | Enzyme-free glucose sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110887882A CN110887882A (en) | 2020-03-17 |
| CN110887882B true CN110887882B (en) | 2021-01-22 |
Family
ID=69750483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911232624.5A Active CN110887882B (en) | 2019-12-05 | 2019-12-05 | Enzyme-free glucose sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110887882B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114939421B (en) * | 2022-07-25 | 2022-10-14 | 苏州中星医疗技术有限公司 | Glucose sensor, glucose catalyst and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5772102B2 (en) * | 2011-03-17 | 2015-09-02 | セントラル硝子株式会社 | Electrode for fluorine compound electrosynthesis |
| CN104716234A (en) * | 2014-12-26 | 2015-06-17 | 南京邮电大学 | Nanometer material with double-frequency light cooperative conversion capability and ink-jet printing film formation method thereof |
| CN107422010B (en) * | 2017-08-11 | 2019-07-30 | 重庆科技学院 | A kind of enzyme-free glucose sensor |
| CN107505372B (en) * | 2017-08-11 | 2019-10-15 | 重庆科技学院 | A kind of preparation method of enzyme-free glucose sensor |
| CN108165270A (en) * | 2018-02-06 | 2018-06-15 | 长春工业大学 | A kind of nanometer of golden shell coats upper conversion nano crystalline substance sandwich and preparation method thereof |
| JP7228776B2 (en) * | 2018-05-22 | 2023-02-27 | パナソニックＩｐマネジメント株式会社 | Active material for fluoride ion secondary battery, and fluoride ion secondary battery using the same |
| CN110530944A (en) * | 2019-08-19 | 2019-12-03 | 广州钰芯传感科技有限公司 | It is a kind of based on the portable minisize glucose of copper-based nano composite construction without enzyme sensing electrode and the preparation method and application thereof |
-
2019
- 2019-12-05 CN CN201911232624.5A patent/CN110887882B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110887882A (en) | 2020-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Design and facile synthesis of mesoporous cobalt nitride nanosheets modified by pyrolytic carbon for the nonenzymatic glucose detection | |
| Gao et al. | Synthesis of Co3O4-NiO nano-needles for amperometric sensing of glucose | |
| CN105628764B (en) | A kind of electrochemical sensor of detection uric acid and its preparation and application | |
| CN106383158B (en) | A kind of hydrogen peroxide based on silver-graphene nano-complex is without enzyme sensor and preparation method thereof | |
| Cao et al. | Ultrathin nanosheet-assembled accordion-like Ni-MOF for hydrazine hydrate amperometric sensing | |
| CN106290498B (en) | Based on PEDOT-rGO-Ni (OH)2The preparation method of the glucose sensor electrode without enzyme of composite nano materials | |
| Tian et al. | Amperometric detection of glucose based on immobilizing glucose oxidase on g-C3N4 nanosheets | |
| He et al. | A direct “touch” approach for gold nanoflowers decoration on graphene/ionic liquid composite modified electrode with good properties for sensing bisphenol A | |
| CN105606684B (en) | A kind of graphene based on protein-single-walled carbon nanotube-nano-Au composite preparation method and applications | |
| Fu et al. | Highly sensitive nonenzymatic glucose sensor based on reduced graphene oxide/ultrasmall Pt nanowire nanocomposites | |
| CN106525943A (en) | Construction method and application of surface protein-embossed self-energized biological fuel cell sensor | |
| Zhang et al. | Hydrophilic antifouling 3D porous MXene/holey graphene nanocomposites for electrochemical determination of dopamine | |
| Liu et al. | Construction of a non-enzymatic glucose sensor based on copper nanoparticles/poly (o-phenylenediamine) nanocomposites | |
| CN111239220B (en) | Preparation method of enzyme-free glucose sensor based on protein as carrier | |
| CN109270140A (en) | The preparation method and application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor | |
| Zhang et al. | In situ attachment of cupric oxide nanoparticles to mesoporous carbons for sensitive amperometric non-enzymatic sensing of glucose | |
| CN105973956B (en) | Detect the complex film modified acetylene black electrode of graphene-cuprous oxide and detection method of vanillic aldehyde in food | |
| Nguyen et al. | Platinum Nanoflower‐Modified Electrode as a Sensitive Sensor for Simultaneous Detection of Lead and Cadmium at Trace Levels | |
| CN110412095A (en) | A kind of load flower ball-shaped copper sulfide-palladium core-shell structure nitrogen-doped graphene composite material and preparation method and application | |
| Meng et al. | The synthesis of carbon/cerium oxide composites clusters with the assistance of the glucaminium-based surfactant and their electrochemical performance in the glucose monitoring | |
| Zhou et al. | A novel electrochemical sensor based on AuPd/UiO-66-NH 2/GN composites for sensitive dopamine detection | |
| Wu et al. | Long-term cell culture and electrically in situ monitoring of living cells based on a polyaniline hydrogel sensor | |
| CN110887882B (en) | Enzyme-free glucose sensor and preparation method thereof | |
| Li et al. | Waste eggshell membrane-templated synthesis of functional Cu 2+–Cu+/biochar for an ultrasensitive electrochemical enzyme-free glucose sensor | |
| CN110568050B (en) | Preparation method of enzyme-free catalytic hydrogen peroxide electrochemical sensor based on flexible electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |