CN110988080A - Flexible oxygen-enriched bio-enzyme electrode and flexible bio-enzyme sensor based on same - Google Patents

Flexible oxygen-enriched bio-enzyme electrode and flexible bio-enzyme sensor based on same Download PDF

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CN110988080A
CN110988080A CN201911337625.6A CN201911337625A CN110988080A CN 110988080 A CN110988080 A CN 110988080A CN 201911337625 A CN201911337625 A CN 201911337625A CN 110988080 A CN110988080 A CN 110988080A
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CN110988080B (en
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封心建
程情青
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Suzhou Biomimetic Materials Science And Engineering Center
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Suzhou University
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Abstract

The invention relates to a flexible oxygen-enriched bio-enzyme electrode which is formed on the surface of a flexible hydrophobic substrate, and comprises a conductive layer positioned on the surface of the flexible hydrophobic substrate, a catalyst layer connected with the conductive layer and a bio-enzyme layer connected with the catalyst layer, wherein the surface of the flexible hydrophobic substrate is provided with a plurality of gaps for oxygen enrichment and transmission, the catalyst layer is used for catalyzing reduction of hydrogen peroxide, and the bio-enzyme layer is used for reacting with a substance to be detected to generate hydrogen peroxide. The flexible oxygen-enriched bio-enzyme electrode takes air as a direct electronic medium, and detection is carried out under a reduction condition, so that endogenous and exogenous interfering substances of organisms are effectively avoided, and more accurate detection of an object to be detected is facilitated.

Description

Flexible oxygen-enriched bio-enzyme electrode and flexible bio-enzyme sensor based on same
Technical Field
The invention relates to the field of sensors, in particular to a flexible oxygen-enriched bio-enzyme electrode and a flexible bio-enzyme sensor based on the same.
Background
The biological enzyme electrode is formed by coating one or more biological enzymes on a sensitive membrane of a common ion selective electrode, and through the catalytic action of the enzymes, a substance to be detected in a test solution diffuses to the enzyme membrane and contacts with an enzyme layer to generate an enzyme catalytic reaction, so that the activity of the substance to be detected is changed and the substance to be detected is responded by the electrode; or the substance is indirectly measured by allowing the analyte to generate ions which are responded to by the electrodes. Some areOrganic matterIn the presence of enzymesCatalysisLower andoxygen gasReaction, evolution of H2O2Dissolved in the internal electrolyte and supplied with the ions concernedThe organic material is measured by measuring the change in concentration of the organic material by the selective electrode. As in electrochemical glucose biosensors, glucose oxidase is the primary recognition element, serving to specifically recognize glucose. The process is as follows2The glucose oxidase can selectively catalyze the glucose to generate the gluconic acid and the hydrogen peroxide. However, in practical applications, it is limited by O in solution2The concentration leads to low detection linearity, and the detection result can not meet the clinical requirement due to the instability of background current in the detection process.
CN 108872344A is an oxygen-enriched nano-bio-enzyme electrode, a sensor device, a preparation method and an application thereof, the oxygen-enriched nano-bio-enzyme electrode is modified with a hollow structure nano-material with an oxygen-enriched function, catalyst particles of hydrogen peroxide and oxidase corresponding to an object to be detected on an electrode substrate, wherein one or more air or oxygen-enriched cavities are arranged inside a hollow structure body. CN 108896634 a discloses an oxygen-enriched anti-interference electrochemical detection method for glucose, which adopts an oxygen-enriched electrochemical detection device to detect, wherein a first surface of a three-phase oxygen-enriched electrode is in contact with air or oxygen, and a second surface is in contact with an electrolyte to increase the oxygen concentration. CN 107632050A discloses an oxygen-enriched anti-interference glucose electrochemical detection method, the principle of which is similar to that in CN 108896634A. CN 104698042 a discloses a superhydrophobic solid-liquid-gas three-phase coexisting bio-enzyme sensor and a preparation method thereof, which provides sufficient oxygen to supply enzymatic reaction by forming a solid-liquid-gas three-phase coexisting state on the surface of a superhydrophobic material. However, in the conventional two-phase sensor, the oxygen is derived from the dissolved oxygen in the solution, but since the oxygen in the solution is limited and the content of the oxygen is gradually reduced as the reaction proceeds, the fluctuation of the oxygen affects the magnitude of the background current and thus affects the enzyme kinetics and the accuracy of the enzyme detection.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a flexible oxygen-enriched bio-enzyme electrode and a flexible bio-enzyme sensor based on the same.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the flexible oxygen-enriched bio-enzyme electrode is formed on the surface of a flexible hydrophobic substrate, and comprises a conductive layer positioned on the surface of the flexible hydrophobic substrate, a catalyst layer connected with the conductive layer and a bio-enzyme layer connected with the catalyst layer, wherein the surface of the flexible hydrophobic substrate is provided with a plurality of gaps for oxygen enrichment and transmission, the catalyst layer is used for catalyzing reduction of hydrogen peroxide, and the bio-enzyme layer is used for reacting with a substance to be detected to generate hydrogen peroxide.
Further, the flexible hydrophobic substrate is a hydrophobic non-conductive material. The hydrophobic non-conductive material is preferably a polymer, the polymer is preferably PDMS, PE, PU and the like, and is more preferably PDMS, and the biocompatibility and flexibility are good.
Further, the contact angle of the flexible hydrophobic substrate with water is 150 degrees or more.
Further, the gap is formed by a number of one-dimensional, two-dimensional or three-dimensional microstructures. Wherein, the 'one-dimensional micron structure' is preferably a linear structure, the 'two-dimensional micron structure' is preferably a sheet structure, and the 'three-dimensional micron structure' is a three-dimensional structure.
Further, the gaps are in the micron range, preferably, the height of the gaps is 10-20 microns, and the spacing is 1-10 microns. Under the synergistic effect of the material of the hydrophobic substrate, which has low surface energy and a micro-nano structure on the surface, the electrode substrate has hydrophobic capability.
Preferably, the gaps are formed by microstructures of three-dimensional shapes, which may be cylindrical, spherical, spatially reticulated, and the like. More preferably, the gap is formed by a plurality of cylinders arranged at intervals, each cylinder has a height of 16 μm and a diameter of 5 μm, and the distance between two adjacent cylinders is 5 μm.
In the present invention, the surface of the flexible hydrophobic substrate has gaps into which water cannot enter, so that the gaps can be used for the concentration and transmission of oxygen.
In the present invention, "formed on the surface of the substrate" means grown or supported on the surface of the substrate. Furthermore, the conducting layer is made of a flexible conducting material, and the material of the conducting layer is one or more of carbon nano tubes, graphene polymers and organic conducting polymers. The organic conductive polymer may be selected from 3, 4-ethylenedioxythiophene monomer, polyimide, etc.
The conductive layer forms a continuous film on the surface of the flexible hydrophobic substrate, and the thickness of the conductive layer is 10-500 nanometers, preferably 100-200 nanometers. By utilizing the conducting layer, the flexible oxygen-enriched bio-enzyme electrode can be connected with an external signal detection device, an electric signal of the reaction of the substance to be detected under the action of the bio-enzyme layer is detected, and the concentration of the substance to be detected is calculated according to the electric signal.
The material of the conducting layer is preferably carbon nano tube and/or graphene, and the carbon nano tube and/or graphene both have good flexibility, cannot break along with the bending of the substrate, and have good flexibility. When a metal film in which metal particles are deposited is used as a conductive layer, the metal film is broken during bending or stretching of the substrate.
In the present invention, the carbon nanotube includes a single-walled carbon nanotube and/or a multi-walled carbon nanotube.
Furthermore, the material of the catalyst layer is one or more of platinum (Pt), gold (Au), copper (Cu), rhodium (Rh) and ruthenium (Ru).
Further, the catalyst layer may be formed by deposition of zero-dimensional nanomaterials, one-dimensional nanomaterials, two-dimensional nanomaterials, or three-dimensional nanomaterials. Preferably, the zero-dimensional nanomaterial is a nanoparticle or nanosphere; the one-dimensional nano material is a nanowire or a nanorod; the two-dimensional nano material is a nano sheet; the three-dimensional nano material is a dendritic nano wire. More preferably, the catalyst layer is formed by deposition of zero-dimensional nanomaterials. More preferably, the catalyst layer is formed by deposition of Pt nanoparticles and Au nanoparticles. After the two are compounded, the detected electric signal has lower background current, and the detection sensitivity and accuracy are improved.
Further, the thickness of the catalyst layer is 100-500 nm, preferably 200 nm.
Further, the biological enzyme layer comprises a biological enzyme solution, and the biological enzyme comprises one or more of glucose oxidase, lactate oxidase, cholinesterase and alcohol oxidase. The corresponding biological enzyme may be selected according to the type of the substance to be detected.
Further, the concentration of the biological enzyme in the biological enzyme solution is 5-20mg/mL, preferably 10 mg/mL.
Furthermore, the solvent of the biological enzyme solution can be selected according to the needs, so that the biological enzyme can be dissolved and the biological activity of the biological enzyme can not be influenced. Preferably water and 10 wt% nafion.
In a specific embodiment of the present invention, the preparation method of the flexible oxygen-enriched bio-enzyme electrode comprises the following steps:
(1) preparing a flexible hydrophobic substrate, wherein one side surface of the flexible hydrophobic substrate is provided with a plurality of micron-sized columnar bodies which are arranged at intervals;
(2) forming a conducting layer on the surface of one side of the flexible hydrophobic substrate with the micron-sized columnar bodies, wherein the conducting layer is a thin film formed by carbon nano tubes, and the thickness of the conducting layer is 10-500 nanometers, preferably 100-200 nanometers;
(3) depositing Pt nano particles and gold nano particles on the surface of one side, away from the flexible hydrophobic substrate, of the conducting layer in sequence by adopting an electrodeposition method to form a catalyst layer;
(4) and loading the biological enzyme solution on the surface of the catalyst layer, which is far away from the conductive layer, so as to form a biological enzyme layer.
Further, in the step (1), the other side surface of the flexible hydrophobic substrate is planar.
Further, in step (1), a flexible hydrophobic substrate is prepared using a hard template method. The manufacturing method of the flexible hydrophobic substrate comprises the following specific steps: and (3) selecting a flexible hydrophobic material, pouring the prepolymer of the flexible hydrophobic material into a silicon template, carrying out thermosetting molding, taking out, cooling, and taking out the molded material to obtain the flexible hydrophobic substrate.
Further, in the step (3), constant potential deposition is carried out under the condition of-0.3V-0V, and the deposition time is 10s-3 min.
Further, in the step (3), a constant current deposition method is adopted, a three-electrode system is adopted, in the three-electrode system, the counter electrode is a platinum wire, and the reference electrode is a saturated calomel electrode.
Further, in the step (2), the supporting method includes dropping, coating, immersing, and the like.
The invention also provides a flexible biological enzyme sensor which comprises the flexible oxygen-enriched biological enzyme electrode.
The flexible biological enzyme sensor can be used for preparing intelligent clothes, flexible wearable equipment and flexible electronic components.
By the scheme, the invention at least has the following advantages:
the invention takes flexible hydrophobic non-conductive material as the substrate, and the gaps can not be soaked by water, so that the gaps can be used for oxygen enrichment and transmission, and the conducting layer, the catalyst layer and the biological enzyme layer are compounded on the gaps, thereby providing a brand-new electrochemical detection method for the object to be detected with strong anti-interference capability, and achieving the purpose of oxygen enrichment of the electrode by utilizing the wettability characteristic of the superhydrophobic microarray substrate. Compared with the existing electrochemical detection technology, the flexible oxygen-enriched bio-enzyme electrode provided by the invention can effectively avoid the interference of endogenous and exogenous interfering substances, and avoid the problem of unstable detection signals caused by oxygen fluctuation in the detection process. During the detection, the oxidant of the flexible oxygen-enriched bio-enzyme electrode comes from oxygen in the air, and the oxygen supply is not only sufficient and constant.
In the invention, the oxygen on the constructed three-phase interface is sufficient and stable, and the analyte to be detected with higher concentration can be detected while the stable background current and the detection accuracy are ensured.
In addition, the oxygen-enriched bio-enzyme electrode provided by the invention is provided with a reasonable structure and material selection, and has good flexibility based on the mutual matching of the flexible hydrophobic substrate, the conductive layer, the catalyst layer and the bio-enzyme layer.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a flexible PDMS substrate;
fig. 2 is an SEM picture of a flexible PDMS substrate;
FIG. 3 is an SEM image of a conductive layer on the surface of a flexible PDMS substrate;
FIG. 4 is an SEM picture of a catalyst layer on the surface of a conductive layer;
FIG. 5 is an SEM picture of a dried bio-enzyme layer on the surface of a catalyst layer;
FIG. 6 is a schematic structural diagram of a flexible oxygen-enriched bio-enzyme glucose bio-electrode of the present invention;
FIG. 7 is a schematic diagram of an oxygen-enriched bio-enzyme glucose bio-electrode;
FIG. 8 shows the results of detection of 0mM to 120mM glucose using the electrode in example 1;
FIG. 9 shows the results of detection of 5. mu.M-0 mM glucose using the electrode in example 1;
FIG. 10 is a graph showing the results of detection of 0mM to 1.6mM of glucose by the common electrode in comparative example 1;
FIG. 11 shows the detection results of the anti-interference test of the electrode according to the present invention;
FIG. 12 shows the results of stability tests of the electrode of the present invention and a conventional electrode;
FIG. 13 is an i-t curve of the electrode in example 2 and its measurement results for different concentrations of glucose;
FIG. 14 shows the results of detecting glucose at different concentrations by the electrode in example 3 and the i-t curves thereof;
description of reference numerals:
1-a flexible PDMS substrate; 2-a conductive layer and a catalyst layer; 3-biological enzyme layer.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a flexible oxygen-enriched biological enzyme sensor which comprises a flexible oxygen-enriched biological enzyme electrode, wherein the flexible oxygen-enriched biological enzyme electrode is formed on the surface of a flexible PDMS substrate, and comprises a conducting layer positioned on the surface of the flexible PDMS substrate, a catalyst layer connected with the conducting layer and a biological enzyme layer connected with the catalyst layer. The surface of the flexible PDMS substrate is provided with an array structure consisting of micron-sized cylinders. The height of the cylinder is 16 μm, the diameter is 5 μm, and the distance between two adjacent cylinders is 5 μm.
As shown in fig. 1, the preparation method of the flexible PDMS substrate is as follows:
the silicon wafer template was immersed in a cyclohexane solution containing trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane (PFOTS) (0.02 vol%) for 1H, removed and dried at 120 ℃ for 1H (FIG. 1 a).
The Sylgrad silicone elastomer base and Sylgrad 184 silicone elastomer curative (corning, germany) were then mixed in a beaker at a weight ratio of 10: 1. After mixing uniformly, it was poured into a prepared silicon template (fig. 1b), baked at 80 ℃ for 2 hours, and then the PDMS film was peeled off (fig. 1c), to obtain a flexible PDMS substrate with a pillar array (fig. 1 d).
The preparation method of the flexible oxygen-enriched bio-enzyme electrode comprises the following steps:
and S1, preparing a conductive layer.
And using the carbon nanotube film obtained by pumping filtration of the single-walled carbon nanotube aqueous solution as a conductive layer. The method comprises the following specific steps: 5mL of the aqueous dispersion of carbon nanotubes (0.00075 wt%) was filtered through a microfiltration membrane having a diameter of 8 μm, and the resulting filter membrane was dried at 60 ℃ for half an hour to obtain a CNT membrane. The CNT film obtained above was cut into a narrow strip of 0.2cm × 1.5cm, immersed in an acetone solution, and then transferred to the surface of a flexible PDMS substrate. The material of the conducting layer can also be other conducting materials, such as wall multi-carbon nano-tubes, graphene and the like.
S2, preparing a catalyst layer.
Immersing the product obtained in step S1 in 10g/L of H2PtCl6In solution (H)2PtCl6、H2O, 1mol/L H2SO4The volume ratio of (1: 1:2) using a super-hydrophobic conductive substrate as a working electrode, adopting a constant potential deposition method, and adopting a three-electrode bodyThe Pt catalyst was electrodeposited on the surface of the CNT film by using a platinum wire as a counter electrode and silver-silver chloride as a reference electrode, and performing electrodeposition for 150 seconds under a voltage of-0.3V with respect to an Ag/AgCl electrode.
After depositing Pt nanoparticles on the surface of the CNT film, gold nanoparticles were deposited on the surface of Pt for 70s using hitachi E-1010 sputtering (99.99%) of a gold target with an applied power of about 30W and a working pressure of 10Pa on the Pt surface.
S3, preparing a biological enzyme layer.
The present invention is exemplified by glucose oxidase, and other types of biological enzymes can be used in practical production, such as: cholinesterase, lactase, and the like.
In the present invention. The preparation method of the glucose oxidase solution comprises the following steps: mixing 8mg/mL glucose oxidase aqueous solution (glucose oxidase (EC 1.1.3.4, available from Toyobo Co., Ltd.; 126000Ug-1), secondary deionized water and 10 wt% nafion aqueous solution according to a volume ratio of 100:96:4, shaking, dropwise adding the obtained glucose oxidase solution onto the surface of the catalyst layer, naturally drying, and preparing the flexible oxygen-enriched biological enzyme glucose bioelectrode.
Fig. 2 to 5 are SEM pictures of the flexible PDMS substrate, the conductive layer on the surface of the flexible PDMS substrate, the catalyst layer on the surface of the conductive layer, and the dried bio-enzyme layer on the surface of the catalyst layer, respectively, and fig. b is an enlarged view of fig. a, from which the morphology of each layer can be clearly seen.
And carrying out electrochemical assembly on the oxygen-enriched biological enzyme glucose biological electrode to obtain the flexible oxygen-enriched biological enzyme sensor. FIG. 7 is a schematic diagram of an oxygen-enriched bio-enzyme glucose bio-electrode. As can be seen from the figure, the electrode has flexibility, bendability and transparency.
Comparative example 1
A common electrode based on a flat PDMS substrate was prepared in a similar manner as in example 1. Except that the flexible oxygen-rich bio-enzyme electrode is formed on the surface of the planar PDMS substrate.
Electrochemical measurements of glucose concentration were performed on the electrodes prepared in the above examples using a CHI 660E electrochemical workstation with a three-electrode system. The FTE or common electrode is used as the working electrode; pt wire was used as the counter electrode. Ag/AgCl was used as reference electrode. All ampere experiments were performed at-0.05V, with a scan rate of 0.05V s-1.
FIGS. 8 to 9 show the results of glucose measurements at different concentrations using the electrode of example 1, and the glucose concentrations from top to bottom in FIG. 8a are 0mM, 15mM, 30mM, 45mM, 60mM, 90mM, and 120mM, respectively. The concentration of glucose in the graph of FIG. 9 corresponds to 0mM, 1. mu.M, 2. mu.M, 3. mu.M, 4. mu.M, and 5. mu.M from top to bottom. As can be seen from FIG. 8a, the corresponding current gradually increases linearly and steadily, as can be seen from FIG. 8b, the upper limit of detection of the electrode of the present invention can be as high as 60mM, as can be seen from FIG. 9b, the lower limit of detection of the electrode of the present invention can be as high as 1 μ M, and the lower limit of detection is lower than that of the existing glucose bio-enzyme detection electrode, indicating that the sensitivity of the electrode of the present invention is high, as can be seen from FIG. 9a, the response current can also show steady and linear increase with the increase of the concentration with the minimal change of the glucose concentration, and FIG. 9b further illustrates that the response current increases with the increase of the concentration and has better linearity, and the result of FIG. 8 shows that the electrode of the.
FIG. 10 shows the results of detecting glucose at different concentrations by the common electrode in comparative example 1, with an upper limit of detection of only 1.6 mM. In FIG. 10, the concentrations of glucose were 0mM, 0.2mM, 0.4mM, 0.6mM, 1.0mM, and 1.6mM, respectively, from the top to the bottom of the curve. As can be seen from FIG. 10a, the conventional electrode has gradually lost linear response capability with glucose added from 0mmol to 1.6mmol, with a maximum detection limit of 0.8mmol (FIG. 10 b).
Because the electrode is in an environment with a great amount of interfering substances in the actual use process, the accuracy of the detection result of the electrode is very important due to a very high selectivity, and a relatively common concentrated interfering substance is selected for detection in the experiment, wherein the method comprises the following steps:
the selectivity test was performed at-0.05V in the presence of 0.1mM interferents, ascorbic acid (ascorbicic), uric acid (uric acid), acetaminophen (acetaminophen), urea (urea), sucrose (sucrose), lactic acid (lactic acid), ethanol (ethanol) and choline (choline). As shown in FIG. 11, the results show that the i-t curves of various interfering substances added before the detection of glucose were overlapped, and no response current was induced, indicating that the electrodes were insensitive to these interfering substances, while glucose was still detected in the presence of the interfering substances (1 mM Glu and 5mM Glu in the figure), indicating that the present invention has a better selectivity in the detection of glucose.
In order to prove that the electrode of the invention can resist oxygen interference, namely the fluctuation of oxygen does not influence the electrode (the background current is always in a constant state, and oxygen concentration experiments are carried out in deoxidized PBS solution by bubbling in argon gas. oxygen in the atmosphere can diffuse into liquid phase while stirring the deoxidized solution. a dissolved oxygen meter (MP516, SANXIN, China) is used for recording the oxygen concentration in the solution. As shown in figure 12, as the oxygen concentration is gradually increased, the current of a common electrode (curve a in the figure) is reduced, because the oxygen can reduce at a cathode to trigger reduction current under the reducing condition, and as the oxygen concentration in the solution is increased, the reduction current is more and more, the common electrode can not be stably kept under the change of the oxygen concentration, on the contrary, as the change of the oxygen concentration, the electrode of the invention (curve b in the figure) can construct a solid-liquid-gas three-phase interface due to the structural particularity, on the interface, the oxygen concentration is consistent with the oxygen concentration in the air, and the change of the dissolved oxygen in the solution has no influence on the electrode of the invention, i.e. a good and stable oxygen-rich environment is not provided for detecting various targets later.
Example 2
A flexible oxygen-rich bio-enzyme electrode was prepared according to the method of example 1, except that only Pt nanoparticles were deposited on the surface of the CNT film in step S2. FIGS. 13a and b are the i-t curves of the electrode and the results of detecting glucose with different concentrations, respectively, and in FIG. 13a, the concentrations of glucose from top to bottom are 0mM, 10mM, 20mM, 25mM, 45mM and 60 mM; as can be seen from the figure, when the catalyst only has Pt nano-particles, the detection upper limit is also much higher than that of the common electrode; but the background current was 16 microamperes, which was higher than the electrode in example 1.
Example 3
A flexible oxygen-enriched bio-enzyme electrode was prepared according to the method of example 1, except that the flexible PDMS substrate with a cylinder array of example 1 was replaced with a flexible PTFE porous membrane substrate. FIGS. 14a and b are the results of detecting glucose with different concentrations in the electrode pair and i-t curves thereof, respectively, in FIG. 14b, the concentrations of glucose from top to bottom are 0mM, 5mM, 10mM, 15mM, 20mM, 25mM, and 30mM, respectively, and it is evident from the graphs that the response current gradually increases with the increase of glucose concentration.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A flexible oxygen-enriched bio-enzyme electrode, characterized in that: the flexible oxygen-enriched bio-enzyme electrode is formed on the surface of a flexible hydrophobic substrate and comprises a conducting layer, a catalyst layer and a bio-enzyme layer, wherein the conducting layer is located on the surface of the flexible hydrophobic substrate, the catalyst layer is connected with the conducting layer, the bio-enzyme layer is connected with the catalyst layer, a plurality of gaps for oxygen enrichment and transmission are formed in the surface of the flexible hydrophobic substrate, the catalyst layer is used for catalyzing reduction of hydrogen peroxide, and the bio-enzyme layer is used for reacting with a substance to be detected to generate hydrogen peroxide.
2. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the flexible hydrophobic substrate is a hydrophobic non-conductive material.
3. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the contact angle between the flexible hydrophobic substrate and water is more than 150 degrees.
4. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the gap is formed by a plurality of one-dimensional microstructures, two-dimensional microstructures, or three-dimensional microstructures.
5. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the height of the gap is 10-20 microns.
6. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the conducting layer is made of one or more of carbon nano tubes, graphene and organic conducting polymers; the thickness of the conductive layer is 10-500 nanometers.
7. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the material of the catalyst layer is one or more of platinum, gold, copper, rhodium and ruthenium; the thickness of the catalyst layer is 100-500 nm.
8. The flexible oxygen-rich bio-enzyme electrode of claim 1, wherein: the biological enzyme layer comprises a biological enzyme solution, wherein the biological enzyme comprises one or more of glucose oxidase, lactate oxidase, cholinesterase and alcohol oxidase.
9. The flexible oxygen-enriched bio-enzyme electrode of claim 8, wherein: in the biological enzyme solution, the concentration of the biological enzyme is 5-20 mg/mL.
10. A flexible bio-enzyme sensor, characterized by: comprising the flexible oxygen-enriched bio-enzyme electrode of any one of claims 1 to 9.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN112858433A (en) * 2021-01-08 2021-05-28 苏州大学 Solid-liquid-gas three-phase biological enzyme photocathode
CN114720332A (en) * 2022-06-08 2022-07-08 深圳市西尔曼科技有限公司 Method for measuring osmotic pressure of culture solution in cell culture and biochemical device
CN116046874A (en) * 2023-02-15 2023-05-02 重庆联芯致康生物科技有限公司 Dynamic alcohol sensor structure and preparation method

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