A neural electrode modified by an atomically dispersed metal catalytic material at an ultra-ordinary temperature and a preparation method thereof

Abstract

The application discloses a nerve electrode modified by an atomic dispersion metal catalytic material under super-temperature and a preparation method thereof, and the preparation method is as follows: roughening treatment is performed on the surface of a metal wire, cleaning, drying, and a nerve electrode base is obtained; polyimide solution is used to coat the other parts of the nerve electrode base except electrode recording sites; an electrochemical three-electrode system constant current mode is used to prepare the interface of the nerve electrode modified by the atomic dispersion metal catalytic material under super-temperature; the electrode can not only increase the effective contact area of the electrode interface and enhance the electron transport capacity, but also can play the high efficient biological catalytic activity of the atomic dispersion metal catalytic material, reduce the inflammatory reaction of the electrode-tissue interface, reduce the formation of scar tissue, greatly improve the biocompatibility of the nerve electrode, and improve the signal quality and detection sensitivity of long-term recording.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of neural electrodes and materials, and relates to a neural electrode modified by an atomic-level dispersed metal catalytic material at an ultra-high temperature and a preparation method. BACKGROUND

[0002] Neural electrodes play a crucial role in neuroscience research and the treatment of nervous system diseases. They are the basic devices for realizing the interface between the brain and machines, and the key is to accurately monitor and manipulate the electrical physiological activity of the nervous system. With the advancement of technology, neural electrodes have played an important role in the diagnosis and treatment of nervous system diseases such as stroke, Parkinson's disease and epilepsy, because these diseases are often closely related to abnormal neural electrical patterns in the brain. Despite a series of breakthroughs and innovations in this field, current clinically applied neural electrode systems still have some significant problems and limitations, especially in terms of signal acquisition sensitivity and long-term stability.

[0003] Current neural electrodes face great challenges. Clinically, neural electrodes are required to cause no significant tissue damage during implantation while ensuring low impedance and high signal acquisition sensitivity. However, because the material stiffness of traditional implantable neural electrodes is much higher than the natural softness of brain tissue, a serious interface mismatch is formed between the electrode and the brain tissue. This mismatch not only may trigger an inflammatory response, but also may cause damage or even death of neurons, thereby reducing treatment effectiveness and signal quality. Because the brain electrical signal itself is weak and has a large background noise, the signal frequency range is wide and is easily affected by environmental electromagnetic interference. At the same time, the low electron transfer efficiency and low charge injection capacity of traditional metal electrodes limit the electron transport between the tissue-electrode interface, further reducing the signal-to-noise ratio and acquisition sensitivity.

[0004] In view of the above challenges, future neural electrodes should focus on the development of new neural electrode materials and design, aiming to improve the signal acquisition capability and long-term stability of the electrode. SUMMARY

[0005] The purpose of the present application is to improve the deficiencies of current neural electrodes and provide a neural electrode modified by an atomic-level dispersed metal catalytic material at an ultra-high temperature.

[0006] The second purpose of the present application is to provide a preparation method of a neural electrode modified by an atomic-level dispersed metal catalytic material at an ultra-high temperature.

[0007] The technical solution of the present application is summarized as follows:

[0008] A preparation method of a neural electrode modified by an atomic-level dispersed metal catalytic material at an ultra-high temperature, comprising the following steps:

[0009] (1) roughening the surface of a metal wire with a diameter of 5-200 microns by sanding, and sequentially performing ultrasonic cleaning with deionized water, acetone, and anhydrous ethanol, and drying to obtain a neural electrode base;

[0010] (2) configuring a polyimide solution and coating the neural electrode base with the polyimide solution to insulate the neural electrode base except for the electrode recording site; or wrapping the neural electrode base with an insulating sleeve to insulate the neural electrode base except for the electrode recording site;

[0011] (3) connecting the neural electrode obtained in step (2) as a working electrode, a platinum electrode as a counter electrode, and Ag / AgCl as a reference electrode into an electrochemical workstation to form a three-electrode system, adding a 0.2-5 mg / mL atomic dispersion metal catalyst material dispersion liquid as an electrodeposition working solution into an electrolytic cell, submerging the recording site, performing constant current deposition under an ultrahigh temperature environment, and allowing the atomic dispersion metal catalyst material to uniformly deposit on the surface of the recording site, and drying to obtain a neural electrode modified with an atomic dispersion metal catalyst material under an ultrahigh temperature environment;

[0012] The preparation steps of the 0.2-5 mg / mL atomic dispersion metal catalyst material dispersion liquid are as follows: adding 0.2-5 mg of an atomic dispersion metal catalyst material into 1 mL of deionized water, and uniformly dispersing the atomic dispersion metal catalyst material by ultrasonic stirring to obtain a 0.2-5 mg / mL atomic dispersion metal catalyst material dispersion liquid;

[0013] The ultrahigh temperature environment is kept at 50-90°C.

[0014] The metal wire is preferably gold, silver, copper, platinum, tungsten, iridium, nickel, platinum-iridium alloy, nickel-titanium alloy, tungsten-platinum alloy, nickel-cobalt alloy, or stainless steel.

[0015] The mass concentration of the polyimide solution is preferably 30%-50%.

[0016] Preferably, the weight average molecular weight of the polyimide is 10,000-100,000; and the solvent of the polyimide solution is N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, or acetone.

[0017] Preferably, the atomic dispersion metal catalyst material is a bimetallic single-atom nanoenzyme M1M2 MANs or a metal-organic framework material M MOFs.

[0018] In the bimetallic single-atom nanoenzyme M1M2 MANs, M1 is selected from Fe, Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce, or Co;

[0019] M2 is selected from Fe, Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce or Co, M1 and M2 are not the same.

[0020] M in the M MOFs is selected from Fe, Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce or Co.

[0021] The frequency of the ultrasound in step (3) is preferably 40 kHz, and the ultrasound time is 5-30 min.

[0022] Preferably, the deposition current of the constant current deposition is 0.01-0.5 A, and the deposition time is 100-1800 s.

[0023] The neural electrode modified by the super-ambient temperature atomically dispersed metal catalytic material prepared by the preparation method.

[0024] Advantages of the present application:

[0025] The atomically dispersed metal catalytic material has stable and efficient biological catalytic activity, and the structure and catalytic active center of the atomically dispersed metal catalytic material can be accurately regulated, which has high selectivity for catalytic reactions and can maintain stable structure and activity for a long time. The raw materials for synthesizing the material are easy to obtain, and the synthesis method is simple. Meanwhile, the neural electrode is modified in a super-ambient temperature environment in the present application. The molecular thermal motion is more intense in the super-ambient temperature environment, and the electrochemical efficiency is higher. Therefore, the use of the atomically dispersed metal catalytic material to modify the neural electrode interface in the super-ambient temperature environment can not only increase the effective contact area of the electrode interface and enhance the electron transport capacity, but also more uniformly modify the material at the recording site of the neural electrode, thereby prolonging the service life of the electrode. The atomically dispersed metal catalytic material can stably exert its biological catalytic activity for a long time, which helps to improve the long-term stability of the neural electrode interface, improve the signal quality and detection sensitivity of long-term recording. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 It is a schematic diagram of an electrodeposition device.

[0027] Figure 2 It is the electrochemical performance of a neural electrode modified by a super-ambient temperature atomically dispersed metal catalytic material.

[0028] Figure 3 It is the structural characterization of a neural electrode modified by a super-ambient temperature atomically dispersed metal catalytic material.

[0029] Figure 4The application relates to an electrophysiological signal acquisition performance of a nerve electrode modified by an atomic-level dispersed metal catalytic material at an ultra-high temperature. DETAILED DESCRIPTION

[0030] Preparation of bimetallic single-atom nanozyme M1M2 MANs: Xiaoyu Liu, Zhen Wan, Ke Chen, et al. Mated-Atom Nanozymes with Efficient Assisted NAD + Replenishment for SkinRegeneratio n.Nano Lett.2024 24(16),4924-4935.

[0031] Preparation of metal-organic framework material M MOFs: W. Wang, L. Zhang, Z. Liu, et al. Selective Methionine Pool Exhaustion Mediated by a Sequential Positioned MOF Nanotransformer for Intense Cancer Immunotherapy. Adv. Mater. 2023, 35, 2211866.

[0032] The electrodepositing device is shown in Figure 1 , wherein 1 is a constant temperature device, 2 is an atomic-level dispersed metal catalytic material dispersion liquid, 3 is an electrolytic cell, 4 is a reference electrode, 5 is a working electrode, 6 is a counter electrode, and 7 is an electrochemical workstation.

[0033] The application will be further described below through specific embodiments

[0034] The nerve electrode modified by the atomic-level dispersed metal catalytic material at an ultra-high temperature comprises but is not limited to a single needle or an array electrode.

[0035] Embodiment 1

[0036] A preparation method of a nerve electrode modified by an atomic-level dispersed metal catalytic material at an ultra-high temperature comprises the following steps:

[0037] (1) The surface of a platinum-iridium alloy wire with a diameter of 100 microns is roughened by polishing with 500-mesh sandpaper, and is sequentially cleaned by ultrasonic cleaning with deionized water, acetone and anhydrous ethanol, and is dried to obtain a nerve electrode base;

[0038] (2) Prepare a 40% polyimide solution (the weight-average molecular weight of polyimide is 10,000-50,000, and the solvent is N,N-dimethylformamide), and use the polyimide solution to coat and insulate the parts of the neural electrode substrate except for the electrode recording site; (or use an insulating sleeve to wrap and insulate the parts of the neural electrode substrate except for the electrode recording site).

[0039] (3) The neural electrode obtained in step (2) is used as the working electrode, the platinum electrode as the counter electrode, and the Ag / AgCl as the reference electrode. They are connected to an electrochemical workstation to form a three-electrode system. A dispersion of atomically dispersed metal catalyst (FeCu MAN) with a concentration of 1 mg / mL is added to the electrolytic cell as the electrodeposition working solution, which covers the recording site. The recording site is submerged and deposited under constant current (deposition current of 0.1A and deposition time of 900s) at ultra-low temperature (constant temperature maintained at 70℃) to uniformly deposit the atomically dispersed metal catalyst on the surface of the recording site. After drying, a neural electrode modified with atomically dispersed metal catalyst at ultra-low temperature is obtained.

[0040] The preparation steps of the atomically dispersed metal catalyst material (FeCu MAN) dispersion with a concentration of 1 mg / mL are as follows: 1 mg FeCu MAN is added to 1 mL of deionized water, and the mixture is stirred while sonicating (sonication frequency 40 kHz, sonication time 10 min) to uniformly disperse the atomically dispersed metal catalyst material, thus obtaining the atomically dispersed metal catalyst material dispersion with a concentration of 1 mg / mL.

[0041] Example 2

[0042] A method for preparing a neural electrode modified with an atomically dispersed metal catalytic material at ultra-low temperature includes the following steps:

[0043] (1) and (2) are the same as in Example 1 (1) and (2);

[0044] (3) The neural electrode obtained in step (2) is used as the working electrode, the platinum electrode as the counter electrode, and the Ag / AgCl as the reference electrode. They are connected to an electrochemical workstation to form a three-electrode system. A dispersion of atomically dispersed metal catalyst (Cu MOF) with a concentration of 1 mg / mL is added to the electrolytic cell as the electrodeposition working solution, which covers the recording site. The recording site is submerged and deposited under constant current (deposition current of 0.1 A and deposition time of 900 s) at ultra-low temperature (constant temperature maintained at 70 °C) to uniformly deposit the atomically dispersed metal catalyst on the surface of the recording site. After drying, a neural electrode modified with atomically dispersed metal catalyst at ultra-low temperature is obtained.

[0045] The preparation steps of the 1 mg / mL atomic dispersion metal catalytic material (Cu MOF) dispersion solution are as follows: 1 mg of Cu MOF is added into 1 mL of deionized water, and the atomic dispersion metal catalytic material is uniformly dispersed by stirring and ultrasonic treatment (ultrasonic frequency 40 kHz, ultrasonic time 10 min) to obtain a 1 mg / mL atomic dispersion metal catalytic material dispersion solution.

[0046] Experiments prove that, by replacing the platinum-iridium alloy in the embodiment with gold, silver, platinum, tungsten, iridium, nickel, nickel-titanium alloy, tungsten-platinum alloy, nickel-cobalt alloy, or stainless steel, other than the embodiment, a kind of atomic dispersion metal catalytic material modified nerve electrode is prepared respectively;

[0047] By replacing Cu in the Cu MOF in the embodiment with Fe, Rh, Pd, Pt, Ni, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce or Co, such as Fe MOF, Rh MOF, Pt MOF, Ni MOF, Zn MOF, Ru MOF, Ir MOF, Cr MOF, Zr MOF, Mo MOF, Re MOF, Au MOF, Cd MOF, Tb MOF, W MOF, Ce MOF, Co MOF, etc., other than the embodiment, a kind of atomic dispersion metal catalytic material modified nerve electrode is prepared.

[0048] Embodiment 3

[0049] A preparation method of a nerve electrode modified by an atomic dispersion metal catalytic material at an ultra-temperature, comprising the following steps:

[0050] (1) The surface of a gold wire with a diameter of 200 microns is roughened by sanding with 500 mesh sandpaper, and is sequentially cleaned by ultrasonic treatment with deionized water, acetone, and anhydrous ethanol, and is dried to obtain a nerve electrode base;

[0051] (2) A polyimide solution (mass concentration 30%) is prepared (the weight average molecular weight of the polyimide is 50,000-80,000, and the solvent is dimethyl sulfoxide), and the polyimide solution is used to coat the nerve electrode base except for the electrode recording site to insulate; (or an insulating sleeve is used to insulate the nerve electrode base except for the electrode recording site)

[0052] (3) taking the neural electrode obtained in step (2) as a working electrode, a platinum electrode as a counter electrode, and Ag / AgCl as a reference electrode, connecting them into an electrochemical workstation to form a three-electrode system, adding a 0.2 mg / mL atomic dispersion metal catalytic material (FeCo MAN) dispersion liquid as an electrodeposition working solution into an electrolytic cell, and submerging the recording site, and then performing constant current deposition (deposition current: 0.5 A, deposition time: 1800 s) in a super-temperature (constant temperature at 50 DEG C) environment, so that the atomic dispersion metal catalytic material is uniformly deposited on the surface of the recording site, dried, and a neural electrode modified by the atomic dispersion metal catalytic material in a super-temperature environment is obtained;

[0053] The preparation steps of the 0.2 mg / mL atomic dispersion metal catalytic material (FeCo MAN) dispersion liquid are as follows: 0.2 mg of FeCo MAN is added into 1 mL of deionized water, and stirred while being ultrasonic (ultrasonic frequency: 40 kHz, ultrasonic time: 5 min), so that the atomic dispersion metal catalytic material is uniformly dispersed, and a 0.2 mg / mL atomic dispersion metal catalytic material dispersion liquid is obtained.

[0054] Example 4

[0055] A preparation method of a neural electrode modified by an atomic dispersion metal catalytic material in a super-temperature environment, comprising the following steps:

[0056] (1) roughening the surface of a copper wire with a diameter of 5 microns by sanding with 500 mesh sandpaper, and then ultrasonic cleaning with deionized water, acetone, and anhydrous ethanol in sequence, and drying to obtain a neural electrode base;

[0057] (2) preparing a polyimide solution (mass concentration: 50%) (the weight average molecular weight of the polyimide is 80,000-100,000, and the solvent is tetrahydrofuran, or acetone can also be selected), and coating the neural electrode base with the polyimide solution to insulate the part other than the electrode recording site; (or using an insulating sleeve to insulate the part other than the electrode recording site of the neural electrode base);

[0058] (3) taking the neural electrode obtained in step (2) as a working electrode, a platinum electrode as a counter electrode, and Ag / AgCl as a reference electrode, connecting them into an electrochemical workstation to form a three-electrode system, adding a 0.2 mg / mL atomic dispersion metal catalytic material (FeCo MAN) dispersion liquid as an electrodeposition working solution into an electrolytic cell, and submerging the recording site, and then performing constant current deposition (deposition current: 0.5 A, deposition time: 1800 s) in a super-temperature (constant temperature at 50 DEG C) environment, so that the atomic dispersion metal catalytic material is uniformly deposited on the surface of the recording site, dried, and a neural electrode modified by the atomic dispersion metal catalytic material in a super-temperature environment is obtained;

[0059] The preparation steps of the 5mg / mL atomic dispersion metal catalytic material (FeMn MAN) dispersion solution are as follows: 5mg FeMn MAN is added into 1mL deionized water, and the atomic dispersion metal catalytic material is uniformly dispersed by stirring and ultrasonic (ultrasonic frequency 40kHz, ultrasonic time 30min) to obtain a 5mg / mL atomic dispersion metal catalytic material dispersion solution;

[0060] Experiments prove that, by replacing copper in the embodiment with silver, platinum, tungsten, iridium, nickel, nickel-titanium alloy, tungsten-platinum alloy, nickel-cobalt alloy or stainless steel, other steps are the same as in the embodiment, and a neural electrode modified by an atomic dispersion metal catalytic material is prepared;

[0061] Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce or Co (M1 in M1M2 MANs) is respectively used to replace Fe in the embodiment;

[0062] Fe, Rh, V, Pd, Pt, Ni, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W or Ce (M2 in M1M2 MANs) is respectively used to replace Mn in the embodiment;

[0063] M1M2 MANs are VFe MAN, PdRh MAN, PtNi MAN, NiZn MAN, ZnCr MAN, IrZr MAN, RePt MAN, AuIr MAN, CdMo MAN, CrCu MAN, ZrCu MAN, TbCe MAN, WTb MAN, CeW MAN, PdRe MAN, PtAu MAN, NiCd MAN, RhV MAN, MnRu MAN, RhMn MAN, CoRu MAN, RhCo MAN, CuRh MAN, MoRu MAN, RhRu MAN, RuPd MAN, etc. Other steps are the same as in the embodiment; and a neural electrode modified by an atomic dispersion metal catalytic material at an ultra-temperature is prepared.

[0064] Comparative Example 1

[0065] A method for preparing a neural electrode interface modified by an atomic dispersion metal catalytic material at room temperature, comprising the following steps:

[0066] (1) and (2) are the same as steps (1) and (2) in Example 1;

[0067] (3) The neural electrode obtained in step (2) is taken as a working electrode, a platinum electrode is taken as a counter electrode, and Ag / AgCl is taken as a reference electrode, which are connected to an electrochemical workstation to form a three-electrode system. A 1 mg / mL atomic dispersion metal catalyst material (FeCu MAN) dispersion liquid is added to an electrolytic cell as an electrodeposition working solution, which covers the recording site. Constant current deposition (deposition current is 0.1 A, and deposition time is 900 s) is carried out at room temperature (temperature is kept at 27 DEG C) to make the atomic dispersion metal catalyst material uniformly deposited on the surface of the recording site. After drying, a neural electrode modified by an atomic dispersion metal catalyst material at room temperature is obtained. The preparation steps of the corresponding atomic dispersion metal catalyst material (FeCu MAN) dispersion liquid are the same as those in Example 1.

[0068] Comparative Example 2

[0069] A method for preparing a neural electrode interface modified by an atomic dispersion metal catalyst material at room temperature, comprising the following steps:

[0070] (1) and (2) are the same as steps (1) and (2) in Example 2.

[0071] (3) The neural electrode obtained in step (2) is taken as a working electrode, a platinum electrode is taken as a counter electrode, and Ag / AgCl is taken as a reference electrode, which are connected to an electrochemical workstation to form a three-electrode system. A 1 mg / mL atomic dispersion metal catalyst material (FeCu MAN) dispersion liquid is added to an electrolytic cell as an electrodeposition working solution, which covers the recording site. Constant current deposition (deposition current is 0.1 A, and deposition time is 900 s) is carried out at room temperature (temperature is kept at 27 DEG C) to make the atomic dispersion metal catalyst material uniformly deposited on the surface of the recording site. After drying, a neural electrode modified by an atomic dispersion metal catalyst material at room temperature is obtained. The preparation steps of the corresponding atomic dispersion metal catalyst material (FeCu MAN) dispersion liquid are the same as those in Example 1.

[0072] Comparative Example 3

[0073] The neural electrode prepared in steps (1) and (2) in Example 1.

[0074] Experimental Example 1

[0075] The neural electrodes prepared in Example 1, Example 2, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are subjected to electrochemical performance test.

[0076] The electrochemical impedance results of the above five kinds of neural electrodes show that the impedance of the neural electrodes prepared in Example 1 and Example 2 is significantly reduced, which is reduced by more than 50% at a characteristic frequency of 1000 Hz, while the impedance of the neural electrode prepared in Comparative Example 1 is only reduced by 24%. The reduction of impedance is beneficial to improve the collection sensitivity of the neural electrode. See Figure 2; In the cyclic voltammetry test, the area surrounded by the curve of the neural electrode prepared by Example 1, Example 2 and Comparative Example 1 is significantly increased, and the charge storage capacity is significantly improved, especially for Example 1 and Example 2, see Figure 2 In summary, the neural electrode modified by the super-ambient temperature atomically dispersed metal catalytic material can be significantly better than the neural electrode modified by the atomically dispersed metal catalytic material at room temperature.

[0077] Experimental Example 2

[0078] The surface structure of the neural electrodes prepared by Example 1, 2 and Comparative Example 3 was characterized. The surface structure of the neural electrode was characterized by scanning electron microscopy, and the results showed that the surface of the neural electrode prepared by Comparative Example 3 was smooth without significant protrusions, and the surface of the neural electrode prepared by Example 1 had a flaky structure; the surface of the neural electrode prepared by Example 2 had uniform spherical nanoparticles, see Figure 3 The structure can increase the contact area of the neural electrode with the brain tissue, increase the active sites, provide more channels for the transmission of electrical signals, and be beneficial to improve the biocompatibility of the neural electrode and the signal acquisition quality.

[0079] Experimental Example 3:

[0080] A biological application of a neural electrode modified by an atomically dispersed metal catalytic material, comprising the following steps:

[0081] (1) Select adult Wistar male rats, anesthetize and skin, expose the skin from the back of the eye to the front of the ear, fix the rat on a stereotaxic instrument, expose the skull, determine the front and back fontanel and the neural electrode implantation position (CA1: front and back + 3.5 mm; side ± 2.5 mm; depth 2 mm), and use a skull drill to drill the skull.

[0082] (2) The neural electrode prepared by Example 1 (implanted in the left CA1) and the neural electrode prepared by Comparative Example 3 (implanted in the right CA1) were used to record the specific brain area electrophysiological signal using the Intan electrophysiological signal recording device after 5 min of stabilization, and the signal was analyzed and processed to compare the signal recording ability of the two electrodes.

[0083] The experiment proved that the amplitude of the local field potential signal collected by the neural electrode prepared by Example 1 was larger, the energy of the signal was stronger in the frequency domain analysis, and the neural electrode prepared by Example 1 could collect neural signals that the neural electrode prepared by Comparative Example 3 could not collect.

[0084] Results (see Figure 4The analysis shows that the local field potential signal amplitude collected by the neural electrode prepared in Example 1 is higher than that of the neural electrode prepared in Comparative Example 3, and the signal energy collected by the neural electrode prepared in Comparative Example 3 is much lower than that of the neural electrode prepared in Example 1, which shows that the neural electrode prepared in Example 1 is superior to the neural electrode prepared in Comparative Example 3 in the local field potential signal collection performance, and helps to provide more possibilities for the field of neural engineering.

[0085] In this experimental example, the animal models include but are not limited to healthy adult mice, rabbits, epilepsy model mice, Parkinson's model mice, etc.

[0086] The implanted specific brain regions include but are not limited to CA1, CA3, M1, M2, etc.

[0087] The experiments show that the neural electrodes prepared in Examples 2, 3 and 4 respectively replace the neural electrode prepared in Example 1 of the present experimental example, and other conditions are the same as the present experimental example, and the analysis shows that the signal collection ability of the neural electrodes prepared in Examples 2, 3 and 4 is similar to that of the neural electrode prepared in Example 1.

Claims

1. A method for preparing a neural electrode modified with an atomically dispersed metal catalytic material at ultra-low temperature, characterized in that: Includes the following steps: (1) The surface of the metal wire with a diameter of 5-200 micrometers was roughened by sanding with sandpaper, and then ultrasonically cleaned with deionized water, acetone and anhydrous ethanol in sequence, and dried to obtain the nerve electrode substrate. (2) Prepare a polyimide solution and use the polyimide solution to coat and insulate the parts of the neural electrode base except for the electrode recording site; or use an insulating sleeve to wrap and insulate the parts of the neural electrode base except for the electrode recording site. (3) The neural electrode obtained in step (2) is used as the working electrode, the platinum electrode as the counter electrode, and Ag / AgCl as the reference electrode. They are connected to an electrochemical workstation to form a three-electrode system. A dispersion of atomically dispersed metal catalyst material with a concentration of 0.2-5 mg / mL is added to the electrolytic cell as the electrodeposition working solution, which covers the recording site. Constant current deposition is performed under ultra-low temperature conditions to uniformly deposit the atomically dispersed metal catalyst material on the surface of the recording site. After drying, a neural electrode modified with atomically dispersed metal catalyst material under ultra-low temperature conditions is obtained. The preparation steps for an atomically dispersed metal catalyst dispersion with a concentration of 0.2-5 mg / mL are as follows: 0.2-5 mg of atomically dispersed metal catalyst is added to 1 mL of deionized water, and the mixture is stirred while sonicated to uniformly disperse the atomically dispersed metal catalyst, thus obtaining an atomically dispersed metal catalyst dispersion with a concentration of 0.2-5 mg / mL. The aforementioned ultra-normal temperature environment is maintained at a constant temperature of 50-90℃; The atomically dispersed metal catalytic material is a bimetallic single-atom nanozyme M1M2 MANs or a metal-organic framework material MMOFs.

2. The preparation method according to claim 1, characterized in that: The metal wire is made of gold, silver, copper, platinum, tungsten, iridium, nickel, platinum-iridium alloy, nickel-titanium alloy, tungsten-platinum alloy, nickel-cobalt alloy, or stainless steel.

3. The preparation method according to claim 1, characterized in that: The mass concentration of the polyimide solution is 30%-50%.

4. The preparation method according to claim 1 or 3, characterized in that the weight average molecular weight of the polyimide is 10,000-100,000; and the solvent of the polyimide solution is N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, or acetone.

5. The preparation method according to claim 1, characterized in that: In the bimetallic single-atom nanozymes M1M2 MANs, M1 is selected from Fe, Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce, or Co; M2 is selected from Fe, Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce, or Co, and M1 and M2 are not the same.

6. The preparation method according to claim 1, characterized in that: The M in the M MOFs is selected from Fe, Cu, Rh, V, Pd, Pt, Ni, Mn, Zn, Ru, Ir, Cr, Zr, Mo, Re, Au, Cd, Tb, W, Ce, or Co.

7. The preparation method according to claim 1, characterized in that: The ultrasound frequency in step (3) is 40 kHz, and the ultrasound time is 5-30 min.

8. The preparation method according to claim 1, characterized in that: The deposition current for the constant current deposition is 0.01-0.5A, and the deposition time is 100-1800 s.

9. A neural electrode modified with an atomically dispersed metal catalytic material prepared according to any one of claims 1-8 at ultra-low temperature.

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