Pyrolytic carbon with super-hydrophobic surface as well as preparation method and application of pyrolytic carbon

Abstract

According to the pyrolytic carbon with the super-hydrophobic surface, firstly, various micro-nano structures are obtained through a laser etching technology, then copper ions are loaded through dopamine chelating, then surface modification is conducted through low-surface-energy substances, and the super-hydrophobic surface containing a copper ion coating is obtained. According to the obtained pyrolytic carbon mechanical valve super-hydrophobic surface, the surface static water contact angle is larger than 150 degrees, the rolling angle is smaller than 10 degrees, when the pyrolytic carbon mechanical valve super-hydrophobic surface makes contact with blood, a nitrosoglutathione donor in the blood is catalyzed by Cu < 2 + > to release NO gas, a gas film which is automatically dissipated and has the anticoagulation function on the super-hydrophobic surface is repaired, the dynamic stability of the gas film is maintained, and the anti-coagulation effect is achieved. NO can inhibit adhesion and activation of platelets, so that the pyrolytic carbon super-hydrophobic surface has a long-acting anticoagulation function, and the pyrolytic carbon super-hydrophobic surface can be applied to anticoagulation modification of the surface of the mechanical valve.

Description

Technical Field

[0001] This invention relates to the preparation of anticoagulant surfaces for medical implant materials, and more specifically to a method for surface modification of pyrolytic carbon based on a liquid-liquid dynamic NO gas film for long-lasting anticoagulation. Background Technology

[0002] With the deepening of population aging and significant changes in lifestyle in my country, the number of patients with valvular heart disease is increasing and trending towards younger ages. When the condition of the heart valves becomes severe, artificial heart valve replacement surgery is required. Currently, the main products used in clinical practice are mechanical valves and bioprosthetic valves; compared with bioprosthetic valves, mechanical valves, represented by pyrolytic carbon, have superior durability and are the mainstream product in clinical practice. However, mechanical valves have poor blood compatibility, requiring patients to take anticoagulants for life after surgery. This not only imposes a heavy economic burden on patients but also easily induces organ bleeding and various complications, ultimately leading to death. Therefore, improving the blood compatibility of the surface of mechanical valves through various modification methods has always been a difficult and hot issue that urgently needs to be addressed in this field.

[0003] Among numerous surface modification methods, superhydrophobic surface modification has attracted much attention due to its simplicity, wide applicability, and great potential. Its mechanism for improving blood compatibility lies in the fact that when a superhydrophobic surface comes into contact with blood, a gas film barrier is directly formed between the material surface and the blood, effectively inhibiting the adhesion and activation of platelets and other microorganisms, thereby achieving good anticoagulant properties. For example, patent document CN115444982A, published on December 9, 2022, discloses a superhydrophobic self-cleaning anticoagulant composite coating material. In this coating material, the titanium dioxide nanotube structure increases the microscopic roughness of the titanium-based metal substrate surface, while the hydrophobic modification layer reduces the surface energy of the material. The synergistic effect of the rough structure and the hydrophobic modification layer constructs a superhydrophobic surface. Although this coating material has good anticoagulant properties and shows promising application prospects as a biomedical material, a common problem that cannot be avoided remains when using superhydrophobic surfaces underwater. Patent document CN112775561A, published on May 11, 2021, discloses a pyrolytic carbon mechanical valve leaflet with a bi-level pattern on its surface and its preparation method. Patent document CN110548174A, published on December 10, 2019, discloses a method for preparing and applying a superhydrophobic pyrolytic carbon surface. Although these two technical solutions also obtain pyrolytic carbon with a superhydrophobic surface, their surface gas film cannot self-repair after dissipation. That is, the gas film will dissipate rapidly in the liquid environment, which will result in the anticoagulation effect being maintained only for a short period of time, failing to meet the clinical need for long-term anticoagulation of mechanical valves. Therefore, it is extremely important to develop a long-lasting superhydrophobic surface with self-repair function. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a method for developing superhydrophobic pyrolytic carbon, which utilizes laser etching technology and dopamine chelation of Cu. 2+ A method combining low surface energy molecular self-assembly was used to obtain Cu-containing molecules on the surface of pyrolytic carbon. 2+ The coating features a superhydrophobic surface. When this superhydrophobic surface comes into contact with blood, it initially forms a gas film due to its superhydrophobic nature, separating the blood from the material surface. However, this gas film dissipates rapidly. As part of the gas film on the material surface gradually disappears, blood comes into contact with the surface, prompting the surface to catalyze the production of endogenous NO, which is then captured by the superhydrophobic surface, replenishing the lost gas film. The formation of a new, complete gas film then, in turn, blocks the flow of Cu from the surface. 2+ Contact, blocking Cu 2+ The catalytic reaction prevents the disorderly growth of the gas film. With the continuous repetition of this process, the dynamic stability of the gas film is maintained for a long time, thus achieving long-term anticoagulant properties.

[0005] This invention proposes a superhydrophobic pyrolytic carbon surface. First, a micro / nano structure is constructed on the surface of the pyrolytic carbon using laser etching. Then, dopamine-chelated copper ions are loaded onto the surface. Finally, a low-surface-energy surfactant is used for surface modification, resulting in a superhydrophobic pyrolytic carbon surface with a static water contact angle greater than 150° and a roll-off angle less than 10°. This makes the entire superhydrophobic surface of the pyrolytic carbon exhibit low-adhesion superhydrophobic properties, thereby reducing the residence time of blood on the surface of the pyrolytic carbon mechanical valve, avoiding turbulence, reducing platelet activation, and lowering the probability of surface thrombus formation.

[0006] In this invention, the micro-nano structure constructed on the surface of the pyrolytic carbon is one of rectangular, pebble-shaped, and grating-shaped structures formed by depressions and protrusions, wherein the protrusions are nanoparticles.

[0007] The low surface energy surfactant is selected from one of perfluorodecyltriethoxysilane, stearic acid, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and tridecafluorooctyltriethoxysilane.

[0008] The above-mentioned method for preparing superhydrophobic pyrolytic carbon includes the following steps:

[0009] Step 1: Fabrication of micro / nano structures on the surface of pyrolytic carbon: Laser etching is used to etch the surface of the pretreated pyrolytic carbon. The laser etching pattern is one of the following: rectangular pattern, pebble pattern, or grating pattern. The spacing between adjacent patterns is 10–100 μm, thereby forming a micro / nano structure composed of depressions and protrusions on the surface of the pyrolytic carbon. The laser etching process employs a region-selective tilted beam processing method. The laser etching parameters are: laser wavelength 1064 nm, power 2–20 W, line scan speed 10–1000 mm / s, and frequency 20 Hz.

[0010] Step 2: Dopamine chelation and copper ion loading on the surface: Dopamine was dissolved in a tris(hydroxymethyl)aminomethane hydrochloride buffer solution at pH 8.5 to form a blend solution with a dopamine concentration of 1 mg / mL. The pyrolytic carbon with micro / nano structures formed on the surface obtained in Step 1 was immersed in the blend solution and reacted for 6–24 h under light protection and stirring at a stirring rate of 100–300 rpm. After the reaction was completed, the surface was rinsed with deionized water, dried, and then placed in a Cu... 2+ In a copper-containing aqueous solution with a concentration of 0.1 mM to 100 mM, the mixture was reacted on a shaker for 6 to 24 hours at a speed of 100 to 300 rpm. After the reaction was completed, the mixture was rinsed with deionized water and dried.

[0011] Step 3: Preparation of superhydrophobic carbon surface by pyrolysis: The surface obtained in Step 2 has Cu... 2+ Pyrolytic carbon was immersed in a low surface energy surfactant solution with a concentration of 0.01 mol / L to 0.2 mol / L for 0.5 to 2 h, dried in a constant temperature oven at 60 to 120 °C for 1 to 6 h, and then cooled to room temperature to obtain a superhydrophobic surface with a static water contact angle greater than 150° and a roll-off angle less than 10° on the surface of the pyrolytic carbon.

[0012] In the preparation method described in this invention, the copper-containing aqueous solution is prepared by dissolving a copper-containing compound in deionized water, wherein the copper-containing compound is CuSO4·5H2O or CuCl2.

[0013] This invention relates to Cu in the pyrolytic carbon superhydrophobic surface 2+ The catalytic GSNO donor releases NO over a long period of time, and the bubbles formed underwater not only actively replenish the gas, thus achieving the self-healing properties of the superhydrophobic coating and improving the stability of the gas film on the superhydrophobic surface, but also inhibit platelet activation and enhance the anticoagulant function of pyrolytic carbon, providing a new technical approach for mechanical valves to achieve excellent blood compatibility over a long period of time.

[0014] The pyrolytic carbon superhydrophobic surface of this invention has a special rectangular, pebble, and grating structure pattern, which is then loaded with dopamine-loaded Cu. 2+After further treatment with a low surface energy material, the surface exhibits superhydrophobic properties with low adhesion. In the presence of GSNO donor blood, it possesses a long-lasting superhydrophobic surface self-healing function, improving superhydrophobic surface stability, thereby reducing blood retention time, preventing turbulence, reducing platelet activation, and lowering the incidence of valve-related complications. The superhydrophobic pyrolytic carbon prepared by the method of this invention can be used to prepare mechanical valves. The prepared mechanical valve contains Cu. 2+ The superhydrophobic surface of the layer, when in contact with blood on the mechanical valve surface, utilizes the Cu on the surface... 2+ The process catalyzes the release of NO gas from nitrosoglutathione (GSNO) in the blood, repairing the gas membrane that automatically dissipates on a superhydrophobic surface and functions as an anticoagulant; the gas membrane blocks Cu from the blood and the surface of the mechanical valve. 2+ Contact, blocking Cu 2+ The catalytic reaction of NO prevents the disorderly growth of the gas film, thus maintaining the dynamic stability of the gas film for a long time and achieving long-term anticoagulant properties. At the same time, NO inhibits platelet adhesion and activation, prolonging clotting time. Attached Figure Description

[0015] Figure 1 These are SEM and contact angle images of the pyrolytic carbon superhydrophobic surface with a rectangular pattern prepared in Example 1;

[0016] Figure 2 These are SEM and contact angle images of the pyrolytic carbon superhydrophobic surface with a pebble pattern prepared in Example 4;

[0017] Figure 3 Cu prepared in Comparative Example 1 2+ Underwater self-healing diagram of superhydrophobic surface of 0 mM pyrolytic carbon;

[0018] Figure 4 The Cu obtained in Example 6 2+ Underwater self-healing diagram of superhydrophobic surface of 0.1 mM pyrolytic carbon;

[0019] Figure 5 The Cu obtained in Example 7 2+ Underwater self-healing diagram of superhydrophobic surface of 1 mM pyrolytic carbon;

[0020] Figure 6 This refers to Cu prepared in Example 8 and Example 1. 2+ Underwater self-healing diagram of a superhydrophobic surface of 10 mM pyrolytic carbon;

[0021] Figure 7 The Cu obtained in Example 9 2+ Underwater self-healing diagram of a superhydrophobic surface of 100 mM pyrolytic carbon;

[0022] Figure 8 This is the Cu element EDS image of the pyrolytic carbon superhydrophobic surface obtained in Example 1;

[0023] Figure 9 This is the Cu element EDS image of the pyrolytic carbon superhydrophobic surface obtained in Example 9;

[0024] Figure 10 The graph shows the hemolysis rate of conventional pyrolytic carbon, pyrolytic carbon prepared in Comparative Example 1 and Example 8.

[0025] Figure 11 The attached diagram shows platelet adhesion of conventionally pyrolytic carbon, pyrolytic carbon prepared in Comparative Example 1, and Example 8.

[0026] Figure 12 The images show the clotting time of conventional pyrolytic carbon, pyrolytic carbon prepared in Comparative Example 1, and pyrolytic carbon prepared in Example 8. Detailed Implementation

[0027] This invention uses pyrolytic carbon as the matrix material and employs laser etching to chelate Cu with dopamine. 2+ The method of combining fluorosilane molecule self-assembly to prepare liquid-borne pyrolytic carbon superhydrophobic surfaces is described. The specific embodiments described are only for explanation and illustration of the present invention and are not intended to limit the present invention.

[0028] Example 1

[0029] The surface modification of pyrolytic carbon involves the following steps:

[0030] Step 1, Pretreatment of pyrolytic carbon: Using pyrolytic carbon as the matrix material, the sample is cut into the required size using wire cutting technology. After polishing with 800#, 2000#, 5000# and 7000# sandpaper in sequence, it is ultrasonically cleaned with ethanol and deionized water for 10-50 min in sequence, and then dried for later use.

[0031] Step 2, Preparation of micro / nano structures on the surface of pyrolytic carbon: Laser etching is used to etch the surface of pyrolytic carbon. The laser etching pattern is designed as a rectangular pattern, with the rectangle spacing set to 20 μm. The laser etching parameters are: laser wavelength of 1064 nm, power of 8 W, line scan speed of 100 mm / s, and frequency of 20 Hz.

[0032] Step 3, loading dopamine: Dissolve dopamine in a buffer solution with a pH of 8.5 at a concentration of 1 mg / mL. Place the material obtained in step 2 into the mixture and react in the dark for 12 h at a stirring speed of 150 rpm. After the reaction, rinse three times with deionized water and dry for later use.

[0033] Step 4, Loading Cu 2+The sample obtained above was placed in a solution containing 10 mM CuSO4·5H2O and reacted on a shaker for 12 h at a speed of 150 rpm. After the reaction was completed, it was rinsed three times with deionized water and dried for later use.

[0034] Step 5, Preparation of superhydrophobic surface of pyrolytic carbon: The surface prepared in step 4 has Cu... 2+ Pyrolytic carbon was immersed in a 0.02 mol / L solution of a low surface energy surfactant, fluorosilane, for 1 hour. Finally, it was dried in a 60°C oven for 6 hours and then cooled to room temperature, resulting in a superhydrophobic pyrolytic carbon surface with a static water contact angle of 162.1° and a roll-off angle of 3.01°. SEM images and contact angle photographs of the surface are shown below. Figure 1 As shown.

[0035] Example 2

[0036] The surface modification of pyrolytic carbon was carried out in Example 2. The preparation process was basically the same as that of Example 1, except that in step 2, the rectangular spacing of the laser etching pattern was changed from 20 μm to 10 μm. The final obtained pyrolytic carbon superhydrophobic surface with a rectangular structure had a contact angle of 156.5° and a roll-off angle of 3.23°.

[0037] Example 3

[0038] The surface modification of pyrolytic carbon was carried out in Example 3, which was basically the same as the preparation process of Example 1, except that in step 2, the rectangular spacing in the laser etching pattern was changed from 20 μm to 100 μm. The final obtained pyrolytic carbon superhydrophobic surface with rectangular structure had a contact angle of 150.3° and a roll-off angle of 3.11°.

[0039] Example 4

[0040] The surface modification of pyrolytic carbon was carried out in Example 4, with the preparation process being basically the same as that of Example 1, except that in step 2, the rectangular structure was changed to a pebble structure with a pebble spacing of 15 μm. Laser spot focusing was performed, the laser wavelength was 1064 nm, the laser output power was set to 10 W, the laser line scanning speed was 100 mm / s, and the frequency was 20 Hz. The sample was aligned with the etching area, and the marking program was started to etch the sample surface. The final obtained pyrolytic carbon superhydrophobic surface with a pebble structure is shown in the SEM and contact angle photographs. Figure 2 As shown, its contact angle is 163.1° and its roll-off angle is 3.02°.

[0041] Example 5

[0042] The surface modification of pyrolytic carbon was carried out in Example 5, which was basically the same as the preparation process of Example 1, except that in step 2, the rectangular structure was changed to a grating structure. The final obtained pyrolytic carbon superhydrophobic surface with a grating structure had a contact angle of 157.3° and a roll-off angle of 3.13°.

[0043] Comparative Example 1

[0044] Cu-free 2+ Preparation and application experiments of pyrolytic carbon superhydrophobic surfaces.

[0045] The preparation process of Comparative Example 1 is basically the same as that of Example 1, except that steps 3 and 4 are not performed. The final pyrolytic carbon superhydrophobic surface has a contact angle of 163.1° and a roll-off angle of 3.04°.

[0046] The obtained superhydrophobic gas film on the pyrolytic carbon surface was partially disrupted, and then placed in a PBS solution containing GSNO donor. The damaged gas film on the material surface did not repair itself. An optical photograph of the underwater self-healing pattern of the superhydrophobic pyrolytic carbon surface in Comparative Example 1 is shown below. Figure 3 As shown, a shows the complete air film, b shows the partially damaged air film, and c shows the air film after recovery.

[0047] Example 6

[0048] Cu 2+ Preparation and application experiments of pyrolytic carbon superhydrophobic surface with a concentration of 0.1 mM.

[0049] The preparation process of Example 6 is basically the same as that of Example 1, except that in step 4, Cu is... 2+ The concentration was changed from 10 mM to 0.1 mM; the final obtained pyrolytic carbon superhydrophobic surface with a rectangular structure had a contact angle of 161.5° and a roll-off angle of 3.10°.

[0050] For the obtained Cu 2+ The superhydrophobic surface film of pyrolytic carbon at a concentration of 0.1 mM was partially disrupted. Subsequently, the material was placed in a PBS solution containing GSNO donor. The damaged film on the material surface was repaired. An optical photograph of the underwater self-healing pattern of the superhydrophobic surface of pyrolytic carbon in Example 6 is shown below. Figure 4 As shown, a) shows the complete air film, b) shows the partially damaged air film, and c) shows the repaired air film.

[0051] Example 7

[0052] Cu 2+ Preparation and application experiments of pyrolytic carbon superhydrophobic surface with a concentration of 1 mM.

[0053] The preparation of Example 7 is basically the same as that of Example 1, except that in step 4, Cu... 2+ When the concentration was changed from 10 mM to 1 mM, a pyrolytic carbon superhydrophobic surface with a rectangular structure was finally obtained, with a contact angle of 162.2° and a roll-off angle of 3.08°.

[0054] The obtained Cu 2+ A 1 mM pyrolytic carbon superhydrophobic surface gas film was partially disrupted, and then placed in a PBS solution containing GSNO donor. The damaged gas film on the material surface was rapidly repaired. An optical photograph of the underwater self-healing pattern of the pyrolytic carbon superhydrophobic surface in Example 7 is shown below. Figure 5 As shown, a shows the complete air film, b shows the partially damaged air film, and c shows the air film after recovery.

[0055] Example 8

[0056] Cu 2+ Application experiments of pyrolytic carbon superhydrophobic surface with a concentration of 10 mM.

[0057] Cu obtained in Example 1 2+ A 10 mM pyrolytic carbon superhydrophobic surface gas film was partially disrupted, and then placed in a PBS solution containing GSNO donor. The damaged gas film on the material surface was rapidly repaired. An optical photograph of the underwater self-healing pattern of the pyrolytic carbon superhydrophobic surface in Example 1 is shown below. Figure 6 As shown, a shows the complete air film, b shows the partially damaged air film, and c shows the air film after recovery.

[0058] Example 9

[0059] Cu 2+ Experiments on pyrolytic carbon superhydrophobic surfaces with a concentration of 100 mM and their applications.

[0060] The preparation of Example 9 is basically the same as that of Example 1, except that in step 4, Cu is used... 2+ When the concentration was changed from 10 mM to 100 mM, a pyrolytic carbon superhydrophobic surface with a rectangular structure was finally obtained, with a contact angle of 160.9° and a roll-off angle of 3.09°.

[0061] For the obtained Cu 2+ The superhydrophobic surface film of pyrolytic carbon at a concentration of 100 mM was partially disrupted. Subsequently, the material was placed in a PBS solution containing GSNO donor, and the damaged film on the material surface was repaired. An optical photograph of the underwater self-healing pattern of the superhydrophobic surface of pyrolytic carbon in Example 9 is shown below. Figure 7 As shown, a shows the complete air film, b shows the partially damaged air film, and c shows the air film after recovery.

[0062] Research Materials

[0063] To investigate Cu 2+ The distribution degree of the pyrolytic carbon superhydrophobic surfaces obtained in Examples 1 and 9 of this invention was measured by SEM. Figure 8 and Figure 9 Example 1 (Cu) is shown. 2+ Concentration of 10 mM) and Example 9 (Cu 2+ The EDS diagram of Cu on the superhydrophobic surface of pyrolytic carbon (concentration of 100 mM) shows that copper ions were successfully loaded on the material surface and were uniformly distributed. Figure 4-7 The results showed that different Cu 2+ Materials at all concentrations can repair partially damaged air films and maintain the dynamic stability of the air film.

[0064] Hemolysis rate is an important indicator for measuring the blood compatibility of artificial heart valves. Figure 10 Hemolysis rate diagrams for Comparative Example 1 and Example 8 are shown. Experimental results indicate that the hemolysis rates of the three groups of materials—conventional pyrolytic carbon, pyrolytic carbon prepared in Comparative Example 1, and pyrolytic carbon prepared in Example 8—are all far below 5%, meeting the requirements for hemolysis rates in implantable medical devices. Compared to pyrolytic carbon without surface modification, the hemolysis rate of the superhydrophobic surface of the pyrolytic carbon obtained in Comparative Example 1 and Example 8 is significantly reduced. Before gas film destruction (A), there was no significant difference between the donor group and the undonated group in Comparative Example 1 and Example 8. After gas film destruction (B), compared to before gas film destruction (A), the hemolysis rates of the donor group and the undonated group in Comparative Example 1 significantly increased. The hemolysis rate of the undonated group in Example 8 also significantly increased, but the hemolysis rate of the donor group significantly decreased. This is because after adding the GSNO donor, Cu... 2+ The catalytic release of NO further reduces the hemolysis rate of the material.

[0065] Assess platelet adhesion on superhydrophobic surfaces of pyrolytic carbon. Figure 11 Platelet adhesion diagrams for Comparative Example 1 and Example 8 are shown. Experimental results indicate that the platelet adhesion on the superhydrophobic surface of pyrolytic carbon obtained in Comparative Example 1 and Example 8 is significantly reduced compared to pyrolytic carbon without surface modification. Before gas film disruption (A), there was no significant difference between the donor group and the non-donor group, and between the pyrolytic carbon group, Comparative Example 1, and Example 8. After gas film disruption (B), compared to before gas film disruption (A), the platelet adhesion in both the donor group and the non-donor group in Comparative Example 1 was significantly increased. The hemolysis rate in the non-donor group of Example 8 was also significantly increased, but the hemolysis rate in the donor group was significantly reduced. This is because Cu... 2+ The catalytic release of NO inhibited platelet adhesion and activation. This indicates that the pyrolytic carbon, after laser etching and Cu loading, [is effective / effective]. 2+ After treatment with low surface energy surfactants, the material can maintain its resistance to platelet adhesion for a long time.

[0066] Clotting time, a key indicator for assessing blood coagulation function, refers to the time required for blood to transition from a non-clotting state to a fully coagulated state after leaving the body. It is used in experiments to screen the activity of different coagulation factors. PT, or prothrombin time, is mainly used to assess the function of the extrinsic coagulation system; TT, or thrombin time, is commonly used in in vitro experiments to measure the coagulation capacity of plasma; APTT, or activated partial thromboplastin time, can more comprehensively reflect the synergistic effects of prothrombin, fibrinogen, and factors V and X in the intrinsic coagulation pathway of blood. Figure 12 The coagulation time graphs for Comparative Example 1 and Example 8 are shown. The experimental results indicate that the APTT time of the superhydrophobic surface of pyrolytic carbon obtained in Comparative Example 1 and Example 8 is significantly prolonged compared with that of unmodified pyrolytic carbon. Before gas film destruction (A), there was no significant difference between the pyrolytic carbon group and the unmodified group, and between the pyrolytic carbon group, Comparative Example 1 group, and Example 8 group. After gas film destruction (B), compared with before gas film destruction (A), the APTT time of the donor group and the unmodified group in Comparative Example 1 was significantly reduced. The APTT time of the unmodified group in Example 8 was significantly reduced, but the APTT time of the donor group was significantly prolonged. The PT and TT experimental results both showed this trend, indicating that the pyrolytic carbon was laser-etched and loaded with Cu. 2+ The treatment of the surface with low surface energy surfactants is of great significance for the development of a pyrolytic carbon mechanical valve with long-term anticoagulation properties.

[0067] Although the present invention has been described above in conjunction with the accompanying drawings, the present invention is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many improvements and changes under the guidance of the present invention without departing from the spirit of the present invention, and these improvements and changes are all within the protection scope of the present invention.

Claims

1. A pyrolytic carbon having a superhydrophobic surface, characterized in that, The micro-nano structure is first constructed on the surface of pyrolytic carbon by a laser etching process, then the surface is subjected to dopamine chelation to load copper ions, and finally the surface is modified by a low surface energy surfactant, so as to obtain the pyrolytic carbon with a super-hydrophobic surface, the static water contact angle of which is greater than 150° and the rolling angle of which is less than 10°.

2. The pyrolytic carbon having a superhydrophobic surface according to claim 1, wherein The micro-nano structure constructed on the surface of the pyrolytic carbon is one of rectangular shape, cobblestone shape and grating shape, and the protrusions are nanoparticles.

3. The pyrolytic carbon having a superhydrophobic surface according to claim 1, wherein The low surface energy surfactant is selected from one of perfluorodecyl triethoxysilane, stearic acid, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, tridecafluorooctyl trimethoxysilane and tridecafluorooctyl triethoxysilane.

4. A method of producing a pyrolytic carbon having a superhydrophobic surface as claimed in any one of claims 1 to 3, characterized in that, The method comprises the following steps: Step one, preparation of the micro-nano structure on the surface of pyrolytic carbon: laser etching is adopted to etch the surface of the pretreated pyrolytic carbon, the laser etching pattern is one of rectangular pattern, cobblestone pattern and grating pattern, the interval between adjacent patterns is 10-100 μm, so as to form the micro-nano structure composed of recesses and protrusions on the surface of the pyrolytic carbon, and the laser etching parameters are as follows: laser wavelength is 1064 nm, power is 2-20 W, line scanning speed is 10-1000 mm / s, and frequency is 20 Hz; Step two, chelate copper ions on the surface by dopamine: dissolve dopamine in a tris-hydroxymethyl aminomethane hydrochloride buffer solution with a pH of 8.5 to form a blend solution with a dopamine concentration of 1 mg / mL, and immerse the pyrolytic carbon with the micro-nano structure on the surface obtained in step one in the blend solution. React for 6-24 h in the dark with stirring at a stirring rate of 100-300 rpm. After the reaction, rinse with deionized water and dry, then place in a Cu 2+ aqueous solution containing copper with a concentration of 0.1 mM-100 mM, and react on a shaker for 6-24 h at a rotation speed of 100-300 rpm. After the reaction, rinse with deionized water and dry. Step three, pyrolytic carbon super-hydrophobic surface preparation: the surface with Cu 2+ of step two is soaked in a low surface energy surfactant solution with a concentration of 0.01 mol / L to 0.2 mol / L, soaked for 0.5 to 2 hours, dried in a constant temperature oven at 60 to 120°C for 1 to 6 hours, and then cooled to room temperature, to obtain a pyrolytic carbon surface with a surface static water contact angle greater than 150° and a rolling angle less than 10°.

5. The method of claim 4, wherein the superhydrophobic surface pyrolytic carbon is prepared by the steps of: The copper-containing aqueous solution is prepared by dissolving a copper-containing compound in deionized water, and the copper-containing compound is CuSO4·5H2O or CuCl2.

6. Use of pyrolytic carbon having a superhydrophobic surface produced by the production method according to claim 4 or 5, characterized in that, The pyrolytic carbon with a super-hydrophobic surface is used to prepare a mechanical valve.

7. Use of a pyrolytic carbon having a superhydrophobic surface according to claim 6, characterized in that The mechanical valve prepared contains Cu 2+ The super-hydrophobic surface of the layer repairs the gas film that automatically dissipates and has an anticoagulation function on the Cu 2+ Catalyzes the release of NO gas in blood nitroso glutathione (GSNO), repairs the gas film that automatically dissipates and has an anticoagulation function on the super-hydrophobic surface; the gas film blocks the blood and the Cu 2+ Contact, blocks the catalytic reaction of Cu 2+ , avoids the disorderly growth of the gas film, and the dynamic stability of the gas film is maintained for a long time, and long-term anticoagulation performance is obtained; at the same time, NO inhibits the adhesion and activation of platelets, prolongs the coagulation time.

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