Metal oxide modified neural electrode and preparation method thereof

By modifying the metal oxide of enzyme activity on the surface of the nerve electrode and wrapping the non-recording site area, the problems of neural electrode biocompatibility and noise interference are solved, and high-sensitivity signal acquisition and long-term stability are achieved, which improves its Application effects in the diagnosis and treatment of brain diseases.

CN119138902APending Publication Date: 2024-12-17TIANJIN UNIV
View PDF 1 Cites 0 Cited by

Patent Information

Application Number
CN202411306638.8
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-09-19
Publication Date
2024-12-17

AI Technical Summary

Technical Problem

Existing neural electrodes are difficult to form good biocompatibility after implantation into the brain, resulting in aggravated inflammatory response and noise interference in electrical signal acquisition, affecting their application effect in the diagnosis and treatment of brain diseases.

Method used

The surface of the nerve electrode is modified by electrochemical deposition using an enzymatic aqueous metal oxide solution, improving biocompatibility and electrochemical properties, and insulating materials are used to wrap the non-recording site areas to reduce noise interference.

Benefits of technology

It significantly improves the biocompatibility and signal acquisition sensitivity of neural electrodes, extends its service life, and ensures long-term stability and high-precision signal detection.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure CN119138902A_ABST
    Figure CN119138902A_ABST
Patent Text Reader

Abstract

The invention provides a metal oxide modified neural electrode and a preparation method thereof, and the preparation method of the neural electrode comprises the following steps: taking a metal oxide aqueous solution with enzymatic activity as an electrodeposition liquid, carrying out electrochemical deposition on a recording site of the electrode, and modifying a metal oxide on the surface of the recording site, and obtaining the neural electrode deposited with the metal oxide.
Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

[0001] The present disclosure relates to the technical field of neural electrodes, and in particular to a neural electrode and a preparation method thereof. Background Art

[0002] With the development of science and technology and the improvement of medical level, as a tool that can record neural signals and send electrical stimulation, neural electrodes play an important role in the diagnosis and treatment of brain diseases such as Alzheimer's disease, Parkinson's syndrome, stroke, epilepsy, sleep dysfunction, etc., and are increasingly used in neuroscience and clinical medicine.

[0003] However, although neural electrodes have shown great application potential and prospects, existing technologies still face many challenges and limitations. Among them, the most prominent problem lies in the compatibility and acquisition performance of neural electrodes. Due to the complexity and particularity of the brain tissue environment, traditional neural electrodes are often difficult to form good biocompatibility with surrounding tissues after implantation, resulting in aggravated inflammatory response, impaired electrode function, and even failure. In addition, the noise interference problem in the acquisition process also seriously affects the quality and accuracy of the signal, limiting the application effect of neural electrodes in fine neural regulation and treatment. Summary of the invention

[0004] In view of this, the main purpose of the present disclosure is to provide a neural electrode and a preparation method thereof, in order to at least partially solve at least one of the above-mentioned technical problems.

[0005] To achieve the above purpose, the technical solution of the present invention is as follows:

[0006] In one aspect of the present disclosure, a method for preparing a neural electrode is provided, comprising:

[0007] An aqueous solution of a metal oxide with enzyme activity is used as an electrochemical deposition solution to perform electrochemical deposition on the recording site of the electrode to modify the metal oxide on the surface of the recording site to obtain a neural electrode deposited with the metal oxide.

[0008] As another aspect of the present disclosure, a neural electrode prepared by the above preparation method is provided, wherein the neural electrode comprises an electrode, and a metal oxide with enzyme activity is modified on the surface of the recording site of the electrode.

[0009] According to the embodiments of the present disclosure, metal oxides with enzymatic activity are modified on the surface of neural electrodes by electrochemical deposition, which effectively reduces neuroinflammation that may be caused by neural electrode implantation and improves the biocompatibility of neural electrodes. The introduction of metal oxides can also increase the electron transfer rate of neural electrodes, improve the electrochemical properties of neural electrodes, and improve the acquisition sensitivity of neural electrodes. In addition, the corrosion resistance and chemical stability of metal oxides also ensure the long-term stability of neural electrodes during use. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a scanning electron microscope image of the neural electrode recording site in Example 1 of the present disclosure;

[0011] Figure 2 It is an electrochemical test diagram of the neural electrodes in Example 1 and Comparative Example 1 of the present disclosure;

[0012] Figure 3 It is an electrochemical test diagram of the nerve electrodes in Example 1 and Comparative Example 2 of the present disclosure;

[0013] Figure 4 It is an electrochemical test diagram of the neural electrodes in Example 3 and Comparative Example 3 of the present disclosure;

[0014] Figure 5 It is the enzyme activity test diagram of the neural electrodes in Example 1 and Comparative Example 2 of the present disclosure. DETAILED DESCRIPTION

[0015] In order to make the objectives, technical solutions and advantages of the present disclosure more clearly understood, the present disclosure is further described in detail below in conjunction with specific embodiments.

[0016] The endpoints and any values ​​of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this disclosure.

[0017] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise", "include", etc. used herein indicate the existence of the features, steps, operations and / or components, but do not exclude the existence or addition of one or more other features, steps, operations or components.

[0018] In the field of neuroscience and medical engineering, existing neural electrodes have problems with insufficient biocompatibility and noise interference during signal acquisition, which limits the high-precision capture and long-term stable monitoring of neural signals. Therefore, it is urgent to develop a neural electrode that has both acquisition sensitivity and biocompatibility, as well as good long-term stability.

[0019] In the process of realizing the concept of the present disclosure, it was found that metal oxides with enzymatic activity have unique biochemical properties. For example, they have antioxidant ability (such as strong antioxidant properties verified by the ABTS method), and can also simulate the functions of key enzymes in the body, such as catalase (CAT), peroxidase (POD) and superoxide dismutase (SOD), thereby effectively reducing neuroinflammatory responses after implantation and significantly improving biocompatibility. Secondly, metal oxides also have good electrocatalytic activity, which can enhance the ability to capture weak and complex neural electrical activities while reducing the interference of background noise, thereby ensuring the quality of detection data. In addition, the corrosion resistance and chemical stability of metal oxide materials enable them to effectively resist the erosion of complex environments in the body. The stability of neural electrodes in long-term monitoring is ensured and their service life is extended, providing strong technical support for long-term, continuous scientific research and clinical research.

[0020] According to an embodiment of one aspect of the present disclosure, a method for preparing a neural electrode is provided, comprising:

[0021] An aqueous solution of a metal oxide with enzyme activity is used as an electrochemical deposition solution to perform electrochemical deposition on the recording site of the electrode to modify the metal oxide on the surface of the recording site to obtain a neural electrode deposited with the metal oxide.

[0022] According to an embodiment of the present disclosure, a metal oxide with enzymatic activity is modified on the surface of a neural electrode by electrochemical deposition. The enzymatic activity of the metal oxide can effectively reduce harmful active molecules at the tissue-electrode interface, thereby reducing neuroinflammation that may be caused after the implantation of the neural electrode and enhancing the biocompatibility of the neural electrode. In addition, the metal oxide has the energy storage mechanism of a supercapacitor, and based on the energy storage mechanism of the Faraday redox reaction, it realizes efficient storage and release of charge, thereby improving the electrochemical properties of the neural electrode and enhancing the sensitivity of the electrode during signal acquisition. The good corrosion resistance and chemical stability of the metal oxide also ensure the stability of the neural electrode in long-term use, thereby extending its service life.

[0023] According to an embodiment of the present disclosure, the method for preparing a neural electrode further includes:

[0024] The area other than the area where the metal oxide is deposited is wrapped with an insulating material. That is, the recording site of the neural electrode is modified by depositing the metal oxide with enzyme activity, and the area other than the recording site is wrapped with an insulating material.

[0025] According to the embodiments of the present disclosure, an insulating material is used to cover the area outside the recording site, which effectively isolates the conductive interference of the area outside the recording site, ensuring that only the recording site part can accurately capture the electrical signal of neural activity, thereby significantly improving the sensitivity and signal-to-noise ratio of the signal, and further improving the accuracy and reliability of signal acquisition. Among them, the insulating material is selected from one of polyimide, polytetrafluoroethylene, and polymethyl methacrylate. Selecting an insulating material with a high dielectric constant and good biocompatibility can effectively isolate the electrical signal interference in non-target areas and enhance the accuracy and stability of signal acquisition. At the same time, it can reduce the immune response with biological tissues and ensure the safety and effectiveness of long-term implantation of neural electrodes in the body.

[0026] According to the embodiment of the present disclosure, before electrochemical deposition is performed on the recording site of the electrode, the recording site of the electrode is also pre-treated, and the pre-treatment includes: roughening treatment. The roughening treatment includes: using 80-600 mesh sandpaper or a sander to grind the recording site to obtain a roughened recording site to ensure its stable bonding with the subsequent deposition layer. Subsequently, the roughened recording site is ultrasonically cleaned and dried with deionized water, acetone and ethanol in turn to remove impurities on the surface of the recording site to obtain a pre-treated recording site.

[0027] According to the embodiments of the present disclosure, the metal oxide with enzyme activity is selected from any one of copper oxide, zinc oxide, manganese tetraoxide, ferric oxide, cobalt oxide, tin oxide, ferrous oxide, zinc cobaltate, copper cobaltate, lithium manganate, copper chromite, and vanadium pentoxide. The enzyme activity of the metal oxide makes it have good biocompatibility, which can significantly reduce the inflammatory response and oxidative stress that may be caused after implantation in the human body, thereby protecting the peripheral nerve tissue from damage. Secondly, the metal oxide also has good electrocatalytic properties, which can enhance the sensitivity of the electrode to weak neural electrical signals, while reducing the interference of background noise, thereby improving the accuracy and reliability of the detection data. In addition, the corrosion resistance and chemical stability of the metal oxide help to protect the performance of the electrode from being affected during long-term monitoring, thereby extending the service life of the electrode.

[0028] According to an embodiment of the present disclosure, the thickness of the metal oxide deposition with enzyme activity is 1 to 10 μm, for example, the thickness can be 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, etc. If the deposition thickness is too thin (<1 μm), the metal oxide layer will not be fully covered and the enzyme active sites will be scarce, thereby weakening the detection sensitivity and catalytic efficiency of neural signals. In addition, too thin deposition is prone to wear and fall off, thereby reducing the stability and durability of the electrode. If the deposition thickness is too thick (>10 μm), the resistance of the neural electrode will increase, the signal transmission will be blocked, thereby reducing the response speed and sensitivity, and reducing the accuracy of signal capture.

[0029] According to the disclosed embodiment, the metal oxide aqueous solution is obtained by dispersing the metal oxide in water and by ultrasonic dispersion treatment. During the ultrasonic dispersion treatment process, the ultrasonic frequency is 10 kHz to 80 kHz, for example, it can be 10kHz, 20 kHz, 30 kHz, 35 kHz, 40 kHz, 50 kHz, 70 kHz, 80 kHz, etc., and the ultrasonic time is 1 to 3 minutes, for example, it can be 1 minute, 1.5 minutes, 2 minutes, 2.5 minutes, 3 minutes, etc. Ultrasonic dispersion improves the dispersibility and stability of the metal oxide in water, and further promotes the uniformity of the deposited layer during its subsequent deposition process. The concentration of the metal oxide aqueous solution is 0.1 to 10 mg / mL, for example, it can be 0.1 mg / mL, 1 mg / mL, 3 mg / mL, 5 mg / mL, 10 mg / mL, etc. When the concentration of the metal oxide aqueous solution is too low, the metal oxide content in the solution is too little, and a longer deposition time is required to complete the deposition, resulting in a decrease in preparation efficiency. When the concentration of the metal oxide aqueous solution is too high, it will lead to the formation of metal oxide clusters during the deposition process, thereby affecting the adhesion firmness of the deposition.

[0030] According to the embodiment of the present disclosure, in order to ensure that the electrode can efficiently and accurately transmit neural signals and has good biocompatibility to reduce stimulation and damage to biological tissues, the material of the electrode is any one of metal or semiconductor silicon, and the diameter is 2 to 600 μm, for example, 2 μm, 50 μm, 100 μm, 300 μm, 600 μm, etc. Among them, the metal is selected from any one of platinum, gold, platinum-iridium alloy, stainless steel, tungsten, and copper.

[0031] According to the embodiments of the present disclosure, the electrochemical deposition method includes any one or more of a constant current deposition method, a constant voltage deposition method or a multi-potential step deposition method. In the electrochemical deposition process, an electrochemical workstation is used and the pretreated recording site is used as a working electrode, a calomel electrode or an Ag / AgCl electrode is selected as a reference electrode, a platinum wire electrode or a carbon rod electrode is selected as a counter electrode, and an aqueous solution of a metal oxide material is used as an electrochemical deposition liquid. The electrochemical deposition liquid is placed in an electrolytic cell after ultrasonic dispersion treatment, and the deposition parameters are adjusted to perform electrochemical deposition on the recording site. Furthermore, a variety of electrochemical deposition methods can be selected to deposit the recording site of the electrode, wherein the deposition current of the constant current deposition method is 0.0001-5 mA, for example, 0.0001 mA, 0.001 mA, 0.01 mA, 0.1 mA, 1 mA, 5 mA, etc.; the deposition voltage of the constant voltage deposition method is 0.01-2 V, for example, 0.01 V, 0.1 V, 1 V, 1.5 V, 2 V, etc.; the deposition voltage of the multi-potential step deposition method is 0.1-2 V, for example, 0.1 V, 0.5 V, 1 V, 1.5 V, 2 V, etc., and the deposition time is 300s-1800s, for example, 300s, 600s, 900s, 1200s, 1800s, etc. By adjusting the deposition parameters and deposition time, the thickness of the metal oxide deposition with enzyme activity can be controlled.

[0032] According to an embodiment of the present disclosure, when the total deposition time of electrochemical deposition exceeds 300s, after each deposition of 300s to 400s, for example, 300s, 350s, 370s, 400s, etc., the electrochemical deposition solution is subjected to ultrasonic dispersion treatment, and then electrochemical deposition is performed. Wherein, the specific steps of ultrasonic dispersion treatment include: placing the metal oxide aqueous solution into a clean container, and then sealing the container mouth. An ultrasonic cleaning machine is used to perform ultrasonic dispersion treatment on the sealed metal oxide aqueous solution, and the energy of ultrasonic waves is used to promote the uniform dispersion of metal oxide particles in the solvent, effectively avoiding the aggregation and agglomeration phenomenon during the electrochemical deposition process, and ensuring that the solution is uniform and stable. During the ultrasonic dispersion treatment process, the ultrasonic frequency is kHz to kHz, for example, kHz, kHz, kHz, kHz, kHz, etc., and the ultrasonic time is 1 to 3 minutes, for example, 1 minute, 1.5 minutes, 2 minutes, 2.5 minutes, 3 minutes, etc.

[0033] According to an embodiment of the present disclosure, the metal oxide aqueous solution can also be dispersed by magnetic stirring, and the specific steps include: adding a clean and sterile magnetic particle to a container containing the metal oxide aqueous solution, then placing the container on a magnetic stirring table, and starting a stirring program. The metal oxide aqueous solution is uniformly stirred and dispersed by using the rotational motion of the magnetic particle.

[0034] According to an embodiment of another aspect of the present disclosure, a neural electrode prepared by the above-mentioned preparation method is provided, wherein the neural electrode comprises an electrode, and a metal oxide with enzyme activity is modified on the surface of the recording site of the electrode.

[0035] According to the embodiment of the present disclosure, the present disclosure introduces a metal oxide material with enzyme activity into the surface of a neural electrode, and the prepared neural electrode has good biocompatibility and electrochemical performance, low electrochemical AC impedance and good charge storage efficiency. In addition, the prepared neural electrode also has excellent stability, which can extend its service life in the human body environment.

[0036] In order to make the purpose, technical scheme and advantages of the present disclosure more clear, the present disclosure is further described in detail below in conjunction with specific embodiments and drawings. Specific techniques or conditions not specified in the embodiments are conventional methods and can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0037] Embodiment 1:

[0038] This embodiment 1 provides a method for preparing a neural electrode, comprising the following steps:

[0039] The recording site of the platinum-iridium electrode with a diameter of 100 μm was polished with 300-grit sandpaper to achieve surface roughening. Then it was ultrasonically cleaned with deionized water, acetone, and ethanol in turn, and dried to obtain the pretreated recording site;

[0040] Using a CHI660E electrochemical workstation and a three-electrode system, the pretreated recording site was used as the working electrode, the Ag / AgCl electrode was used as the reference electrode, the platinum wire electrode was used as the counter electrode, and a 0.5 mg / mL aqueous solution of copper cobaltate (CuCo2O4) was used as the electrodeposition solution. The electrodeposition solution was ultrasonically dispersed and placed in an electrolytic cell. The constant current deposition method was used with a deposition current of 0.0001 mA and a deposition time of 300 s to electrochemically deposit the recording site, and a neural electrode with CuCo2O4 deposited on the recording site was obtained;

[0041] The area of ​​the nerve electrode other than the area where CuCo2O4 is deposited is coated and wrapped with a polyimide insulating material to obtain a nerve electrode S1.

[0042] Figure 1 It is a scanning electron microscope image of the neural electrode recording site in Example 1 of the present disclosure.

[0043] like Figure 1 As shown, uniform and dense CuCo2O4 particles are attached to the surface of the recording site of the neural electrode S1, indicating that CuCo2O4 has been successfully deposited on the surface of the recording site.

[0044] Embodiment 2:

[0045] This embodiment 2 provides a method for preparing a neural electrode, comprising the following steps:

[0046] The recording site of the platinum-iridium electrode with a diameter of 150 μm was polished with 360-grit sandpaper to achieve surface roughening. Then it was ultrasonically cleaned with deionized water, acetone, and ethanol in sequence, and dried to obtain the pretreated recording site;

[0047] Using a CHI660E electrochemical workstation and a three-electrode system, the pretreated recording site was used as the working electrode, the Ag / AgCl electrode was used as the reference electrode, the platinum wire electrode was used as the counter electrode, and a 0.2 mg / mL copper chromite (CuCr2O4) aqueous solution was used as the electrodeposition solution. The electrodeposition solution was ultrasonically dispersed and placed in an electrolytic cell. The constant current deposition method was used with a deposition current of 0.0005 mA and a deposition time of 300 s to electrochemically deposit the recording site, and a neural electrode with CuCr2O4 deposited on the recording site was obtained;

[0048] The area on the nerve electrode other than the area where CuCr2O4 is deposited is coated and wrapped with a polyimide insulating material to obtain a nerve electrode S2.

[0049] Embodiment 3:

[0050] This embodiment 3 provides a method for preparing a neural electrode, comprising the following steps:

[0051] The recording site of the platinum-iridium electrode with a diameter of 100 μm was polished with 300-grit sandpaper to achieve surface roughening. Then it was ultrasonically cleaned with deionized water, acetone, and ethanol in turn, and dried to obtain the pretreated recording site;

[0052] Using a CHI660E electrochemical workstation and a three-electrode system, the pretreated recording site was used as the working electrode, the Ag / AgCl electrode was used as the reference electrode, the platinum wire electrode was used as the counter electrode, and a 0.5 mg / mL CuCo2O4 aqueous solution was used as the electrodeposition solution. The electrodeposition solution was ultrasonically dispersed and placed in an electrolytic cell. A constant current deposition method was used, with a deposition current of 0.0001 mA and a deposition time of 600 s. After 300 s of electrochemical deposition, the deposition process was paused, the electrodeposition solution was placed in a clean container, and then the container mouth was sealed. The sealed electrodeposition solution was ultrasonically dispersed using an ultrasonic cleaner. The treated electrodeposition solution was then poured back into the electrolytic cell, and the deposition process was continued for the remaining 300 s to obtain a neural electrode with CuCo2O4 deposited on the recording site.

[0053] The area on the nerve electrode other than the area where CuCo2O4 is deposited is coated and wrapped with a polyimide insulating material to obtain a nerve electrode S3.

[0054] Comparative Example 1:

[0055] This comparative example 1 provides a method for preparing a neural electrode, comprising the following steps:

[0056] The recording site of the platinum-iridium electrode with a diameter of 100 μm was polished with 300-grit sandpaper to achieve surface roughening. Then it was ultrasonically cleaned with deionized water, acetone, and ethanol in turn, and dried to obtain the pretreated recording site;

[0057] Using a CHI660E electrochemical workstation and a three-electrode system, the pretreated recording site was used as the working electrode, the Ag / AgCl electrode was used as the reference electrode, the platinum wire electrode was used as the counter electrode, and a 0.5 mg / mL CuCo2O4 aqueous solution was used as the electrodeposition solution. The electrodeposition solution was directly placed in the electrolytic cell without ultrasonic dispersion. The constant current deposition method was used with a deposition current of 0.0001 mA and a deposition time of 300 s to electrochemically deposit the recording site, and a neural electrode with CuCo2O4 deposited on the recording site was obtained;

[0058] The area of ​​the nerve electrode other than the area where CuCo2O4 was deposited was coated and wrapped with polyimide insulating material to obtain the nerve electrode D1.

[0059] Comparative Example 2:

[0060] The non-recording site area of ​​the 100 μm platinum-iridium electrode surface without any treatment was coated and wrapped with polyimide insulating material to obtain the neural electrode D2.

[0061] Comparative Example 3:

[0062] This comparative example 3 provides a method for preparing a neural electrode, comprising the following steps:

[0063] The recording site of the platinum-iridium electrode with a diameter of 100 μm was polished with 300-grit sandpaper to achieve surface roughening. Then it was ultrasonically cleaned with deionized water, acetone, and ethanol in turn, and dried to obtain the pretreated recording site;

[0064] Using a CHI660E electrochemical workstation and a three-electrode system, the pretreated recording site was used as the working electrode, the Ag / AgCl electrode was used as the reference electrode, the platinum wire electrode was used as the counter electrode, and a 0.5 mg / mL CuCo2O4 aqueous solution was used as the electrodeposition solution. The electrodeposition solution was directly placed in the electrolytic cell without ultrasonic dispersion. The constant current deposition method was used, with a deposition current of 0.0001 mA and a deposition time of 600 s. The ultrasonic dispersion technology was not performed every 300 s, and the recording site was electrochemically deposited to obtain a neural electrode with CuCo2O4 deposited on the recording site.

[0065] The area on the nerve electrode other than the area where CuCo2O4 was deposited was coated and wrapped with polyimide insulating material to obtain nerve electrode D3.

[0066] The electrochemical performance tests of the neural electrodes in Example 1, Example 3 and Comparative Examples 1 to 3 were performed, including: electrochemical AC impedance test and cyclic voltammetry test. The specific test method is: constructing a three-electrode system under room temperature to test the electrochemical performance of the corresponding neural electrodes. A platinum electrode was used as a counter electrode, an Ag / AgCl electrode was used as a reference electrode, and the neural electrodes in Example 1, Example 3 and Comparative Examples 1 to 3 were used as working electrodes, and a 1×PBS phosphate buffer with a pH value of 7.4 was used as an electrolyte.

[0067] In electrochemical impedance spectroscopy, the test frequency range is 1 Hz~10 5 Hz, wait for the system open circuit voltage to stabilize, apply an AC signal disturbance with an anti-disturbance amplitude of 10 mV to the working electrode, and test the electrochemical AC impedance.

[0068] In the cyclic voltammetry test, the scan rate was set to 50 mV s -1 The potential was scanned in the range of -0.6 V to 0.8 V for two cycles. The charge storage capacity was calculated by integrating the current in the potential range of -0.6 V to 0.8 V of the cyclic voltammetry curve in the second cycle.

[0069] Figure 2 It is the electrochemical test diagram of the nerve electrodes in Example 1 and Comparative Example 2 of the present disclosure.

[0070] like Figure 2 As shown, compared with the neural electrode in comparative example 2, the electrochemical AC impedance of the neural electrode in example 1 is significantly reduced, and the charge storage capacity is increased, which proves that the electrochemical performance of the neural electrode modified by CuCo2O4 material deposition is improved.

[0071] Figure 3 It is the electrochemical test diagram of the nerve electrodes in Example 1 and Comparative Example 1 of the present disclosure.

[0072] like Figure 3 As shown, compared with the neural electrode in comparative example 1, the electrochemical AC impedance of the neural electrode in embodiment 1 is reduced, while the charge storage capacity is increased. Ultrasonic dispersion treatment can effectively promote the uniform dispersion of metal oxides in aqueous solution, reduce the agglomeration phenomenon during the deposition process, and thus optimize the electrochemical properties of the neural electrode.

[0073] Figure 4 It is the electrochemical test diagram of the neural electrodes in Example 3 and Comparative Example 3 of the present disclosure.

[0074] like Figure 4 As shown, compared with the neural electrode in Comparative Example 3, the electrochemical AC impedance of the neural electrode in Example 3 is reduced, while the charge storage capacity is increased. During the electrochemical deposition process, the metal oxide aqueous solution is subjected to ultrasonic dispersion treatment every 300 s of deposition, and the energy of ultrasound is used to promote the uniform dispersion of the metal oxide particles in the solvent, effectively avoiding the aggregation and agglomeration of the metal oxide particles during the electrochemical deposition process, and ensuring the uniformity and stability of the solution. The interface contact quality between the deposited layer and the substrate is improved. The microstructural uniformity and electrochemical activity of the electrode are enhanced, thereby achieving a reduction in electrochemical AC impedance and an increase in charge storage capacity.

[0075] The total antioxidant capacity (ABTS) and peroxidase (POD) activity tests were performed on the neural electrodes in Example 1 and Comparative Example 2 of the present disclosure. Both the ABTS kit and the POD kit were produced by Shanghai Biyuntian Biotechnology Co., Ltd. The test methods of the two kits follow the instructions of the kits, and the absorbance of each experimental group and the control group at a specific wavelength at different reaction times is measured using a microplate reader or a UV-visible spectrophotometer. Among them, the ABTS test measures the absorbance at 414 nm, and the lower the absorbance, the stronger the antioxidant activity of the neural electrode; the POD test measures the absorbance at 652 nm, and the higher the absorbance, the better the peroxidase activity of the neural electrode.

[0076] Figure 5 It is the enzyme activity test diagram of the neural electrodes in Example 1 and Comparative Example 2 of the present disclosure.

[0077] like Figure 5As shown, the ABTS activity and POD activity of Example 1 are higher than those of Comparative Example 2, indicating that the neural electrode modified with CuCo2O4 material has good total antioxidant activity and peroxidase-like activity, which can reduce the dangerous active molecules at the tissue-electrode interface to minimize the neural inflammatory response, thereby improving the biocompatibility of the neural electrode.

[0078] The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present disclosure. It should be understood that the above description is only a specific embodiment of the present disclosure and is not intended to limit the present disclosure. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present disclosure should be included in the protection scope of the present disclosure.

Claims

1. A method for preparing a neural electrode, comprising: An aqueous solution of a metal oxide with enzyme activity is used as an electrochemical deposition solution to perform electrochemical deposition on the recording site of the electrode to modify the metal oxide on the surface of the recording site to obtain a neural electrode deposited with the metal oxide.

2. The preparation method according to claim 1, further comprising: The area other than the area where the metal oxide is deposited is wrapped with an insulating material, wherein: The insulating material is selected from one of polyimide, polytetrafluoroethylene and polymethyl methacrylate.

3. The preparation method according to claim 1, wherein The electrochemical deposition method includes any one or more of a constant current deposition method, a constant voltage deposition method or a multi-potential step deposition method, and the deposition time is 300s to 1800s.

4. The preparation method according to claim 1 or 2, wherein: When the total deposition time of the electrochemical deposition exceeds 300 s, the electrochemical deposition solution is subjected to ultrasonic dispersion treatment after each deposition of 300 s to 400 s.

5. The preparation method according to claim 3, wherein: The metal oxide with enzyme activity is selected from any one of copper oxide, zinc oxide, manganese tetraoxide, ferric oxide, cobalt tetraoxide, tin oxide, ferrous oxide, zinc cobaltate, copper cobaltate, lithium manganate, copper chromite, and vanadium pentoxide; The thickness of the metal oxide deposition with enzyme activity is 1-10 μm.

6. The preparation method according to claim 3, wherein: The aqueous solution of the metal oxide with enzyme activity is obtained by dispersing the metal oxide with enzyme activity in water and subjecting it to ultrasonic dispersion treatment. The concentration of the aqueous solution of metal oxides having enzyme activity is 0.1-10 mg / mL.

7. The preparation method according to claim 1, wherein The electrode is made of any one of metal or semiconductor silicon, and has a diameter of 2 μm to 600 μm; wherein, The metal is selected from any one of platinum, gold, platinum-iridium alloy, stainless steel, tungsten and copper.

8. The preparation method according to claim 1 or 3, wherein: During the ultrasonic dispersion treatment, the ultrasonic frequency is 10 kHz to 80 kHz, and the ultrasonic time is 1 to 3 minutes.

9. The preparation method according to claim 1, before electrochemical deposition is performed on the recording site of the electrode, further comprising: Preprocessing the recording site of the electrode, wherein the preprocessing includes: roughening; The roughening treatment includes: using 80-600 mesh sandpaper or a sander to grind the recording site to obtain a roughened recording site.

10. A neural electrode prepared by the preparation method according to any one of claims 1 to 9, wherein: The neural electrode comprises an electrode, and a metal oxide with enzyme activity is modified on the surface of the recording site of the electrode.

Citation Information

Patent Citations

  • Nanometer material modified neural electrode and preparation method thereof

    CN115813399A