CN117405748A - Flexible stretchable biosensor and preparation method and application thereof - Google Patents
Flexible stretchable biosensor and preparation method and application thereof Download PDFInfo
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- CN117405748A CN117405748A CN202311713722.7A CN202311713722A CN117405748A CN 117405748 A CN117405748 A CN 117405748A CN 202311713722 A CN202311713722 A CN 202311713722A CN 117405748 A CN117405748 A CN 117405748A
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- 239000010931 gold Substances 0.000 claims abstract description 98
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052737 gold Inorganic materials 0.000 claims abstract description 95
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 76
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229960003351 prussian blue Drugs 0.000 claims abstract description 62
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/1468—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
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- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Medical Informatics (AREA)
- Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention provides a flexible stretchable biosensor and a preparation method and application thereof, and relates to the technical field of sensors. The preparation method of the flexible stretchable biosensor comprises the following steps: preparing a three-electrode working system or a two-electrode working system on the surface of the flexible stretchable substrate in a stretched state; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode; the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode. The biosensor manufactured by the flexible substrate has the characteristics of flexibility and stretchability, is suitable for flexible wearable equipment, and can adapt to a narrower and more tortuous and complex environment.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a flexible stretchable biosensor and a preparation method and application thereof.
Background
In biosensors using oxidoreductase as a sensing mechanism, indirect detection of substrates is mostly achieved by hydrogen peroxide generated when the oxidoreductase catalyzes the oxidation of their substrates, i.e. the detection of hydrogen peroxide generated during the oxidation of the enzyme substrates is achieved indirectly by detecting them by electrochemical oxidation methods. For example, glucose is detected by detecting the concentration of glucose oxidase that catalyzes the production of hydrogen peroxide and lactic acid is detected by detecting the concentration of lactate oxidase that catalyzes the production of hydrogen peroxide.
The electrochemical method is widely used for measuring hydrogen peroxide because of the advantages of high sensitivity, rapid reaction, trace detection and high accuracy. For example, chinese patent CN 103336043A discloses a method for preparing hydrogen peroxide biosensor, which comprises the following steps: polishing the glassy carbon electrode by using gamma-alumina powder to clean the surface of the glassy carbon electrode; dispersing graphene in a chitosan-acetic acid solution to obtain a graphene-chitosan black suspension; coating black suspension on a glassy carbon electrode to obtain a graphene-chitosan/glassy carbon electrode; placing the graphene-chitosan/glassy carbon electrode in ionic liquid ethane containing cobalt chloride, and performing electrodeposition to obtain a cobalt nano ion/graphene-chitosan/glassy carbon electrode; dissolving hemoglobin into chitosan-acetic acid solution to obtain chitosan solution of hemoglobin; drying cobalt nano ion/graphene-chitosan/glassy carbon electrode of the chitosan solution coated with hemoglobin in the air to form a film to obtain a target modified electrode, namely a hydrogen peroxide biosensor; the sensor has the advantages of high sensitivity, good biocompatibility and saving of the acquisition cost of the biosensor.
With the development of science, the flexible wearable electronic product is applied to a wearable human health monitoring and nursing system, has the functions of monitoring human movement and preventing diseases, and is therefore receiving more and more attention. However, the existing hydrogen peroxide electrochemical biosensors are all rigid structures, cannot be used for flexible wearable products or implanted in vivo, and limit the application of the hydrogen peroxide electrochemical biosensors.
Disclosure of Invention
The invention aims to provide a flexible stretchable biosensor, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a flexible stretchable biosensor, which comprises the following steps:
preparing a three-electrode working system or a two-electrode working system on the surface of the flexible stretchable substrate in a stretched state; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode;
in the three-electrode working system or the two-electrode working system, the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
Preferably, the flexible stretchable substrate comprises polytetrafluoroethylene, polydimethylsiloxane, polyacrylate, silicone rubber, latex, polyurethane, parylene, or polyimide.
Preferably, when the working electrode is a gold electrode, the method for preparing the working electrode comprises the following steps: evaporating or sputtering a gold film on the surface of the flexible stretchable substrate in a stretching state to obtain a gold electrode;
when the working electrode is a platinum electrode, the preparation method of the platinum electrode comprises the following steps: evaporating or sputtering a platinum film on the surface of the flexible stretchable substrate in a stretched state to obtain a platinum electrode;
when the working electrode is a gold/Prussian blue electrode, the preparation method of the working electrode comprises the following steps: evaporating or sputtering a gold film on the surface of the flexible stretchable substrate in a stretching state, electroplating Prussian blue on the surface of the gold film to form a Prussian blue coating, and obtaining a gold/Prussian blue electrode;
when the working electrode is a platinum/Prussian blue electrode, the preparation method of the working electrode comprises the following steps: evaporating or sputtering a platinum film on the surface of the flexible stretchable substrate in a stretched state, and electroplating Prussian blue on the surface of the platinum film to form a Prussian blue coating, thereby obtaining the platinum/Prussian blue electrode.
Preferably, when the working electrode is a gold electrode or a platinum electrode, the thickness of the gold electrode or the platinum electrode is 20-500 nm; when the working electrode is a gold/Prussian blue electrode or a platinum/Prussian blue electrode, the Prussian blue is a nanoparticle attached to a gold film or a platinum film.
Preferably, when the flexible stretchable biosensor is a three-electrode working system, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a gold electrode or a platinum electrode;
when the flexible stretchable biosensor is a two-electrode working system, the reference/counter electrode is a silver/silver chloride electrode or a gold electrode.
Preferably, the preparation method of the silver/silver chloride electrode comprises the following steps: evaporating or sputtering a silver film on the surface of the flexible stretchable substrate in a stretched state, and soaking the silver film in ferric chloride solution to form a silver/silver chloride electrode.
Preferably, after the working electrode is obtained, the method further comprises the step of immobilizing specific enzymes on the surface of the working electrode.
The invention provides the flexible stretchable biosensor prepared by the preparation method, which comprises a flexible stretchable substrate and a three-electrode working system or a two-electrode working system positioned on the surface of the flexible stretchable substrate; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode;
in the three-electrode working system or the two-electrode working system, the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
The invention provides application of the flexible stretchable biosensor in wearable equipment.
The invention provides application of the flexible stretchable biosensor in detecting hydrogen peroxide, glucose, lactic acid, uric acid, creatinine, cholesterol or triglyceride for non-disease diagnosis and treatment.
The invention provides a preparation method of a flexible stretchable biosensor, which comprises the following steps: preparing a three-electrode working system or a two-electrode working system on the surface of the flexible stretchable substrate in a stretched state; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode; in the three-electrode working system or the two-electrode working system, the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
The biosensor manufactured by the flexible substrate has the characteristics of flexibility and stretchability, is suitable for flexible wearable equipment, and can adapt to a narrower and more tortuous and complex environment.
The working electrode of the biosensor contains gold or platinum and has higher hydrogen peroxide detection sensitivity.
Drawings
FIG. 1 is a flow chart of one process for preparing a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 2 is a flow chart of one of the preparation processes of the flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 3 is another flow chart of the preparation of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 4 is an isometric view of a biosensor of a wrinkle-free three-electrode working system;
FIG. 5 is a transverse fold isometric view of a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 6 is a transverse fold elevation view of a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 7 is a longitudinal fold isometric view of a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 8 is a longitudinal fold elevation view of a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 9 is an oblique fold isometric view of a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 10 is a diagonal, pleated elevation view of a flexible stretchable biosensor of the three-electrode working system of the present invention;
FIG. 11 is an isometric view of a biosensor of a wrinkle-free two-electrode working system;
FIG. 12 is a transverse fold isometric view of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 13 is a transverse fold elevation view of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 14 is a longitudinal fold isometric view of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 15 is a longitudinal fold elevation view of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 16 is an oblique fold isometric view of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 17 is a diagonal fold elevation view of a flexible stretchable biosensor of the two-electrode working system of the present invention;
FIG. 18 is a sample schematic of an electron beam evaporation coater;
FIG. 19 is a photograph of an unstretched gold-evaporated electrode under a high power microscope;
FIG. 20 is a photograph of an evaporated gold electrode under a high power microscope in a stretched state;
FIG. 21 is a photograph of a double electrode wiring scheme measurement of a gold-plated PDMS film electrode;
FIG. 22 shows the results of a chronoamperometric detection of non-stretched electrodes during evaporation;
FIG. 23 shows the current increase and H of the unstretched electrode during gold plating 2 O 2 Linearly fitting the concentration;
FIG. 24 shows the results of a 13% stretched electrode under natural conditions for vapor deposition using chronoamperometry;
FIG. 25 shows the tensile strength of 13% at the time of vapor deposition, the current increase amount at the time of natural condition detection, and H 2 O 2 Linearly fitting the concentration;
FIG. 26 shows the results of measuring 13% tensile strength of a 13% tensile electrode by chronoamperometry during vapor deposition;
FIG. 27 shows the current increase and H at 13% elongation at vapor deposition and 13% elongation at detection 2 O 2 The concentration was linearly fitted to the results.
Detailed Description
The invention provides a preparation method of a flexible stretchable biosensor, which comprises the following steps:
preparing a three-electrode working system or a two-electrode working system on the surface of the flexible stretchable substrate in a stretched state; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode; the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
In the present invention, the flexible stretchable substrate preferably comprises polytetrafluoroethylene, polydimethylsiloxane, polyacrylate, silica gel, rubber, latex, polyurethane, parylene or polyimide, more Preferably Dimethylsiloxane (PDMS). The flexible stretchable substrate has the characteristics of good elasticity, flexibility, biological contact, good stability and the like, and can completely recover the original shape after being bent.
In the invention, the thickness of the flexible stretchable substrate is preferably 5 μm to 5mm, and in the embodiment of the invention, PDMS is specifically 0.5mm.
In the present invention, the elongation of the flexible stretchable substrate in a stretched state is preferably 1 to 100%, more preferably 10 to 50%, and in the embodiment of the present invention, specifically 13%. In the present invention, the elongation refers to (length of the flexible stretchable substrate in a stretched state-length in a natural state)/length in a natural state.
The three-electrode working system will be described first.
In the present invention, the three-electrode working system includes a working electrode, a reference electrode, and a counter electrode.
In the present invention, the working electrode includes a gold electrode, a platinum electrode, a gold/prussian blue electrode, or a platinum/prussian blue electrode.
When the working electrode is a gold electrode, the preparation method of the working electrode comprises the following steps: and evaporating or sputtering a gold film on the surface of the flexible stretchable substrate in a stretched state to obtain the gold electrode.
In the present invention, the vapor deposition method is preferably thermal vapor deposition or electron beam vapor deposition; the sputtering is preferably magnetron sputtering; in the present invention, the thickness of the gold electrode is preferably 20 to 500nm, more preferably 50 to 200 nm. In an embodiment of the present invention, the working electrode is a gold electrode, and the thickness is 60nm. The invention has no special requirements on the evaporation and sputtering conditions, and the evaporation and sputtering conditions well known in the art are adopted.
In the present invention, before the gold film is evaporated or sputtered, it preferably further comprises evaporating or sputtering an adhesion layer on the surface of the flexible stretchable substrate, and the adhesion layer is preferably a Cr film or a Ti film; the thickness of the Cr film or the Ti film is preferably 2-20 nm, and in the embodiment of the invention, the thickness of the Ti film is specifically 5nm. The invention firstly evaporates the adhesive layer to increase the adhesive force of the gold film, so that the electrode is firmer and more reliable.
When the working electrode is a platinum electrode, the preparation method of the platinum electrode comprises the following steps: evaporating or sputtering a platinum film on the surface of the flexible stretchable substrate in a stretched state to obtain the platinum electrode.
In the present invention, the evaporation method or sputtering method used in evaporating the platinum film is the same as above, and will not be described here again. In the present invention, the thickness of the platinum electrode is the same as that of the gold electrode, and will not be described here again. The method of the invention has no special requirements on the evaporation and sputtering modes, and the evaporation and sputtering modes well known in the art can be adopted.
In the present invention, before the evaporating or sputtering the platinum film, it is preferable to further include evaporating or sputtering an adhesion layer on the surface of the flexible stretchable substrate; the adhesion layer is preferably a Cr film or a Ti film. The thickness of the adhesion layer is the same as that of the gold electrode, and the description thereof is omitted.
When the working electrode is a gold/Prussian blue electrode, the preparation method of the working electrode comprises the following steps: and evaporating or sputtering a gold film on the surface of the flexible stretchable substrate in a stretched state, electroplating Prussian blue on the surface of the gold film to form a Prussian blue coating, and obtaining the gold/Prussian blue electrode.
In the present invention, the process of evaporating or sputtering the gold film has been previously discussed, and will not be repeated here. In the invention, the thickness of the gold film is preferably 20-500 nm, more preferably 50-200 nm; the Prussian blue coating is preferably a nanoparticle attached to a gold film. The conditions for plating Prussian blue are not particularly required, and the conditions known in the art are adopted, so that the method is not particularly limited.
When the working electrode is a platinum/Prussian blue electrode, the preparation method of the working electrode comprises the following steps: evaporating or sputtering a platinum film on the surface of the flexible stretchable substrate in a stretched state, and electroplating Prussian blue on the surface of the platinum film to form a Prussian blue coating, thereby obtaining the platinum/Prussian blue electrode.
In the present invention, the process of evaporating or sputtering the platinum film has been previously discussed, and will not be described here again. The conditions for plating Prussian blue are not particularly required, and the conditions known in the art are adopted, so that the method is not particularly limited. In the present invention, the Prussian blue plating layer is preferably nanoparticles attached to a platinum film.
The working electrode of the biosensor contains gold or platinum and has higher hydrogen peroxide detection sensitivity.
In the present invention, the reference electrode is preferably a silver/silver chloride electrode; the preparation method of the silver/silver chloride electrode preferably comprises the following steps: evaporating or sputtering a silver film on the surface of the flexible stretchable substrate in a stretched state, and soaking the silver film in ferric chloride solution to form a silver/silver chloride electrode.
In the present invention, before the evaporation or sputtering of the silver film, it is preferable to further include evaporation or sputtering of an adhesion layer on the surface of the flexible stretchable substrate, and then evaporation or sputtering of a gold or platinum film; the adhesion layer is preferably a Cr film or a Ti film. The thickness of the adhesion layer is the same as that of the gold electrode, and the description thereof is omitted. The invention is used for evaporating or sputtering an adhesion layer and then evaporating or sputtering a gold or platinum film, thereby being beneficial to improving the adhesion of the silver/silver chloride electrode on the substrate. The preparation conditions of the silver/silver chloride electrode are not particularly required, and the preparation conditions well known in the art are adopted.
In the present invention, the counter electrode is preferably a gold electrode or a platinum electrode. The preparation methods of the gold electrode and the platinum electrode are already discussed above, and are not described in detail here.
The two-electrode working system is described below.
In the present invention, the two-electrode working system comprises a working electrode and a reference/counter electrode; the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode; the reference/counter electrode is a silver/silver chloride electrode or a gold electrode.
In the present invention, the preparation method of the working electrode and the preparation methods of the silver/silver chloride electrode and the gold electrode have been discussed above, and will not be described here again.
After the working electrode is obtained, the present invention preferably further comprises immobilizing a specific enzyme on the surface of the working electrode. In the present invention, the specific enzyme is preferably determined according to the detection object of the flexible stretchable biosensor; specifically, a glucose oxidase for detecting glucose; or, a lactate oxidase for detecting lactic acid; or, uricase for detecting uric acid; or, creatine amino hydrolase and creatine oxidase mixture for detecting creatinine; or cholesterol oxidase for detecting cholesterol; or, a mixture of lipases, glycerol kinases and glycerol phosphate oxidase for triglycerides. The method and the amount of the immobilized specific enzyme are not particularly required, and the immobilization method and the immobilization amount which are well known in the art are adopted.
FIG. 1 is a flow chart of one process for preparing a flexible stretchable biosensor of the three-electrode working system of the present invention; as shown in fig. 1, the method comprises the following steps: 1) Stretching the flexible substrate; 2) Manufacturing a working electrode and a counter electrode: evaporating or sputtering metal chromium (Cr) or titanium (Ti) as an adhesion layer on the flexible substrate through a mask plate containing three electrode holes on the surface of the flexible stretchable substrate in a stretching state, then evaporating or sputtering a gold (Au) or platinum (Pt) film, and then electroplating Prussian blue on the surface of the gold or platinum film in the working electrode holes to form a Prussian blue plating layer, thereby obtaining a gold/Prussian blue working electrode or a platinum/Prussian blue working electrode and a gold or platinum counter electrode; 3) Manufacturing a reference electrode: the method comprises the steps that a silver film is evaporated or sputtered on the surface of a gold or platinum film evaporated or sputtered on the flexible substrate in the last step through a mask plate containing an electrode hole, the silver film is soaked in ferric chloride solution to form a silver/silver chloride electrode, and a reference electrode is obtained; 4) Immobilizing a specific enzyme on the working electrode; 5) Releasing the stretching force.
FIG. 2 is a flow chart of one of the preparation processes of the flexible stretchable biosensor of the two-electrode working system of the present invention; the method comprises the following steps: 1) Stretching the flexible substrate; 2) Manufacturing a working electrode: the method comprises the steps of (1) evaporating or sputtering metal chromium (Cr) or titanium (Ti) on a flexible substrate through a mask plate containing two electrode holes on the surface of the flexible stretchable substrate in a stretching state to serve as an adhesion layer, then evaporating or sputtering a gold or platinum film, and electroplating Prussian blue on the surface of the gold or platinum film of the working electrode holes in the adhesion layer to form a Prussian blue coating to obtain a working electrode; 3) Reference/counter electrode fabrication: evaporating or sputtering a silver film on the gold or platinum film evaporated or sputtered in the previous step through a mask plate containing an electrode hole on the surface of the flexible stretchable substrate in a stretching state, soaking the silver film in ferric chloride solution to form a silver/silver chloride electrode, and obtaining a reference electrode; 4) Immobilizing a specific enzyme on the working electrode; 5) Releasing the stretching force.
FIG. 3 is another flow chart of the preparation of a flexible stretchable biosensor of the two-electrode working system of the present invention; the method comprises the following steps: 1) Stretching the flexible substrate; 2) Manufacturing work, reference/counter electrode: the method comprises the steps of (1) evaporating or sputtering metal chromium (Cr) or titanium (Ti) on a flexible substrate through a mask plate containing two electrode holes on the surface of the flexible stretchable substrate in a stretching state to serve as an adhesion layer, then evaporating or sputtering a gold or platinum film, and electroplating Prussian blue on the surface of the gold or platinum film to form a Prussian blue coating to obtain a working electrode and a reference/counter electrode; 4) Immobilizing a specific enzyme on the working electrode; 5) Releasing the stretching force.
The preparation sequence of each electrode is not particularly required, any electrode can be prepared first, and the preparation sequence can be adjusted according to actual conditions by a person skilled in the art. In the present invention, the specific enzyme may be immobilized before or after releasing the stretching force, and the preparation process of fig. 1 to 3 is only illustrative and not representative of the only preparation process.
The invention provides the flexible stretchable biosensor prepared by the preparation method, which comprises a flexible stretchable substrate and a three-electrode working system or a two-electrode working system positioned on the surface of the flexible stretchable substrate; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode;
in the three-electrode working system or the two-electrode working system, the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
FIG. 4 is an isometric view of a biosensor of a wrinkle-free three-electrode working system; FIG. 5 is a transverse fold isometric view of a flexible stretchable biosensor of the three-electrode working system of the present invention; FIG. 6 is a transverse fold elevation view of a flexible stretchable biosensor of the three-electrode working system of the present invention; FIG. 7 is a longitudinal fold isometric view of a flexible stretchable biosensor of the three-electrode working system of the present invention; FIG. 8 is a longitudinal fold elevation view of a flexible stretchable biosensor of the three-electrode working system of the present invention; FIG. 9 is an oblique fold isometric view of a flexible stretchable biosensor of the three-electrode working system of the present invention; FIG. 10 is a diagonal fold elevation view of a flexible stretchable biosensor of the three-electrode working system of the present invention.
FIG. 11 is an isometric view of a biosensor of a wrinkle-free two-electrode working system; FIG. 12 is a transverse fold isometric view of a flexible stretchable biosensor of the two-electrode working system of the present invention; FIG. 13 is a transverse fold elevation view of a flexible stretchable biosensor of the two-electrode working system of the present invention; FIG. 14 is a longitudinal fold isometric view of a flexible stretchable biosensor of the two-electrode working system of the present invention; FIG. 15 is a longitudinal fold elevation view of a flexible stretchable biosensor of the two-electrode working system of the present invention; FIG. 16 is an oblique fold isometric view of a flexible stretchable biosensor of the two-electrode working system of the present invention; FIG. 17 is a diagonal fold elevation view of a flexible stretchable biosensor of the two-electrode working system of the present invention.
The present invention utilizes hydrogen peroxide oxidation or reduction at the working electrode to produce a change in the current signal. The magnitude of the current signal change is proportional to the concentration of the analyte, so that the detection of hydrogen peroxide is realized.
The flexible stretchable substrate has the characteristics of good elasticity, flexibility, biological contact, good stability and the like, and can completely recover the original shape after being bent.
The working electrode of the biosensor contains gold or platinum and has higher hydrogen peroxide detection sensitivity.
The invention provides application of the flexible stretchable biosensor in detecting hydrogen peroxide, glucose, lactic acid, uric acid, creatinine, cholesterol or triglyceride for non-disease diagnosis and treatment.
The method of the present invention is not particularly limited to the described application methods, and application methods well known in the art may be employed. Specifically, when the sensor is used for detecting hydrogen peroxide, a voltage of-0.6V is applied between a working electrode and a reference electrode of the flexible stretchable biosensor, so that the working electrode contacts a solution to be detected, the current increment is measured, and the hydrogen peroxide concentration is calculated according to the linear relation between the hydrogen peroxide concentration and the current increment.
In the present invention, the linear relation between the hydrogen peroxide concentration and the current increase is preferably obtained by the following method: firstly, dropwise adding hydrogen peroxide with different concentrations on a working electrode, obtaining a time-current curve through a traditional timing current method, and then performing linear fitting on the stabilized concentration c and the stabilized current increment delta I according to the time-current curve to obtain the linear relation between the hydrogen peroxide concentration and the current increment.
The invention provides application of the flexible stretchable biosensor in flexible wearable electronic products.
The flexible stretchable biosensor, the method of preparing the same and the application thereof, provided by the present invention, will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The evaporation process is completed in Beijing university micromachining laboratory, 4 non-stretching states and 1 stretching state, the PDMS substrate (thickness 0.5 mm) is stretched, the length before stretching is 30mm, the length of the stretching state is 34mm, the elongation is 13%, electron beam evaporation is carried out in the stretching state, the coated metal material is Ti/Au, the thickness is 5/60nm, namely, 5nm Ti is firstly evaporated, then 60nm Au is evaporated, and 4 samples after evaporation are shown in figure 18.
As can be seen from FIG. 18, the results using an electron beam evaporation coater were satisfactory and the sample color formation was uniform.
The mask was removed and observed under a high power microscope using a 10X objective lens, and fig. 19 and 20 are views of gold deposited under a microscope in unstretched and stretched states, respectively.
The four figures in fig. 19 are four parts of the electrode, a is the boundary corner of the rectangular electrode and the square wiring part, b is one corner below the square wiring part, c is the visual image of the gold electrode, and d is the boundary of the gold electrode. Some cracks appear in the figure, and through the comprehensive inspection of the electrode, the broken place is not found, so that the circuit can be conducted, the evaporation boundary is clear, and the gold film plated in an advanced electronic book film plating mode is compact and uniform, so that the use requirement of the electrode is met.
When gold is evaporated, the PDMS film is in a stretched state, and is removed from the mask plate after gold plating, and the PDMS film is in a natural state, and because the flexibility of the gold is far smaller than that of the PDMS film, the gold forms a plurality of folds in the stretching direction, such as a and b in fig. 20, particularly the folds at the boundary of the gold electrode are clearly visible. And it can be seen that cracks occur in the direction perpendicular to the crease, because there is a stress in the lateral direction when the PDMS film is restored to its original state, so that cracks occur in the gold in the direction perpendicular to the crease, but it does not completely break the gold, and can be used normally.
In fig. 20 c, d are observations in the stretched state, the lateral wrinkles disappeared, particularly at the boundary, but almost longitudinal wrinkles appeared, because the width of PDMS was narrowed during stretching, causing the gold electrode to be pressed toward the middle, and the wrinkles as shown in the figure appeared.
Performance test:
the double-electrode connection mode is used:
as shown in fig. 21, the working electrode signal line of the electrochemical workstation is connected to the working electrode of the sample (the tip of one of the slivers); the counter and reference electrode signal lines are connected to both the reference/counter electrode (the top end of the other elongate strip of sample).
The same operation mode as that of the standard electrode is measured by adopting a timing current method, the potential is set to be 0.6V, the time is 9999s, the clamping current is 1mA, firstly, 30 mu L of phosphoric acid buffer solution is dripped on the working electrode to obtain a current base line, and after the current is stable, 3 mu L of phosphoric acid buffer solution with the concentration of 1 mmol.L is dripped -1 H of (2) 2 O 2 After the current was stabilized, 3. Mu.L of the solutions were added dropwise to the solution at concentrations of 2, 10, 20, 40, 60, 80, and 100 mmol.L, respectively -1 H of (2) 2 O 2 And (3) obtaining a time current curve detected by a timing current method of the gold-plated PDMS film electrode by the solution.
Detection result of non-stretching electrode during vapor deposition
The time-current curve obtained by the chronoamperometry is shown in fig. 22.
The linear regression equation is y= 318.64x-122.92, r= 0.99205, and the linear correlation is strong as shown in fig. 23 by linear fitting the stabilized concentration c and the stabilized current increment Δi.
The correlation coefficient R reveals the quality of the results of each experiment. The results show that the concentration after stabilization and the increase of the stabilizing current have strong linear correlation under the condition of no stretching, which indicates that the method can be used for detecting the concentration of hydrogen peroxide.
Detection of tensile 13% electrode during vapor deposition
(1) Detection result under natural condition
The time-current curve obtained by the chronoamperometry is shown in fig. 24.
The stabilized concentration c and the stabilized current increment Δi were linearly fitted, and the result is shown in fig. 25, where the linear regression equation y= 266.87x-206.21, r, r= 0.9712. The correlation coefficient R reveals the quality of the results of each experiment, and the results show that the sensor prepared in a stretching state is in a natural state, the linear correlation between the concentration after stabilization and the increase of the stabilizing current is strong, and the sensor can be used for detecting the concentration of hydrogen peroxide.
(2) Test results under 13% stretch
The time-current curve obtained by the chronoamperometry is shown in fig. 26.
The stabilized concentration c and the stabilized current increment Δi were linearly fitted, and the result is shown in fig. 27, where the linear regression equation y= 151.825x-51.89, and r= 0.98858. The sensor prepared in the stretching state has strong linear correlation between the concentration after stabilization and the increase of the stabilizing current when in the stretching state, and can be used for detecting the concentration of hydrogen peroxide.
Investigation of electrode detection Range
To explore the H that the electrode can detect 2 O 2 Minimum concentration of 1 mmol.L -1 H of (2) 2 O 2 Diluted 10 times, 100 times and 10 times00 times to 0.001, 0.01 and 0.1 mmol.L -1 H of (2) 2 O 2 Detecting by chronoamperometry, and dripping at concentrations of 0.001, 0.01, 0.1, 1, 2, and 10mmol.L -1 H of (2) 2 O 2 The results are shown in Table 1.
TABLE 1 detection of lower H concentration by non-stretching electrode during vapor deposition 2 O 2 Concentration and current relationship
| Numbering device | Original concentration mmol.L -1 | Mixed concentration mmol.L -1 | Stabilizing current nA | Signal current nA |
| 0 | 0 | 0 | 2.927 | 0 |
| 1 | 0.001 | 0.0000909 | 2.862 | -0.065 |
| 2 | 0.01 | 0.000917 | 2.674 | -0.253 |
| 3 | 0.1 | 0.008538 | 3.491 | 0.564 |
| 4 | 1 | 0.079357 | 15.12 | 12.193 |
| 5 | 2 | 0.2074 | 38.77 | 35.843 |
| 6 | 10 | 0.819438 | 123.641 | 120.714 |
The results in Table 1 show that although the drop concentration was 0.001, 0.01H 2 O 2 mmol·L -1 Peak signals can be generated, but their steady currents are almost the same, and the steady currents do not follow H 2 O 2 The concentration increased and increased, so the lowest concentration detected was considered 0.008538 mmol.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a flexible stretchable biosensor, comprising the steps of:
preparing a three-electrode working system or a two-electrode working system on the surface of the flexible stretchable substrate in a stretched state; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode;
in the three-electrode working system or the two-electrode working system, the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
2. The method of making according to claim 1, wherein the flexible stretchable substrate comprises polytetrafluoroethylene, polydimethylsiloxane, polyacrylate, silicone rubber, latex, polyurethane, parylene, or polyimide.
3. The method of manufacturing according to claim 1, wherein when the working electrode is a gold electrode, the method of manufacturing the working electrode comprises the steps of: evaporating or sputtering a gold film on the surface of the flexible stretchable substrate in a stretching state to obtain a gold electrode;
when the working electrode is a platinum electrode, the preparation method of the platinum electrode comprises the following steps: evaporating or sputtering a platinum film on the surface of the flexible stretchable substrate in a stretched state to obtain a platinum electrode;
when the working electrode is a gold/Prussian blue electrode, the preparation method of the working electrode comprises the following steps: evaporating or sputtering a gold film on the surface of the flexible stretchable substrate in a stretching state, electroplating Prussian blue on the surface of the gold film to form a Prussian blue coating, and obtaining a gold/Prussian blue electrode;
when the working electrode is a platinum/Prussian blue electrode, the preparation method of the working electrode comprises the following steps: evaporating or sputtering a platinum film on the surface of the flexible stretchable substrate in a stretched state, and electroplating Prussian blue on the surface of the platinum film to form a Prussian blue coating, thereby obtaining the platinum/Prussian blue electrode.
4. The method according to claim 1 or 3, wherein when the working electrode is a gold electrode or a platinum electrode, the thickness of the gold electrode or the platinum electrode is 20 to 500nm; when the working electrode is a gold/Prussian blue electrode or a platinum/Prussian blue electrode, the Prussian blue is a nanoparticle attached to a gold film or a platinum film.
5. The method of claim 1, wherein when the flexible stretchable biosensor is a three-electrode working system, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a gold electrode or a platinum electrode;
when the flexible stretchable biosensor is a two-electrode working system, the reference/counter electrode is a silver/silver chloride electrode or a gold electrode.
6. The method of manufacturing according to claim 5, wherein the method of manufacturing a silver/silver chloride electrode comprises the steps of: evaporating or sputtering a silver film on the surface of the flexible stretchable substrate in a stretched state, and soaking the silver film in ferric chloride solution to form a silver/silver chloride electrode.
7. The method according to any one of claims 1 to 3, further comprising immobilizing a specific enzyme on the surface of the working electrode after the working electrode is obtained.
8. The flexible stretchable biosensor prepared by the preparation method of any one of claims 1-7, comprising a flexible stretchable substrate and a three-electrode working system or a two-electrode working system positioned on the surface of the flexible stretchable substrate; the three-electrode working system comprises a working electrode, a reference electrode and a counter electrode; the two-electrode working system comprises a working electrode and a reference/counter electrode;
in the three-electrode working system or the two-electrode working system, the working electrode comprises a gold electrode, a platinum electrode, a gold/Prussian blue electrode or a platinum/Prussian blue electrode.
9. Use of the flexible stretchable biosensor of claim 8 in a wearable device.
10. Use of the flexible stretchable biosensor of claim 8 for detecting hydrogen peroxide, glucose, lactic acid, uric acid, creatinine, cholesterol or triglycerides for non-disease diagnostic and therapeutic purposes.
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