CN115814143A - Anti-adhesion antibacterial suture line, anti-coagulation antibacterial titanium-nickel alloy material and preparation method - Google Patents

Abstract

The invention relates to an anti-adhesion antibacterial suture, an anticoagulant antibacterial titanium-nickel alloy material and a preparation method to solve the problem of exposing poor biocompatibility surfaces during use in reducing the adsorption of implant materials, thereby Loss of anticoagulant and antibacterial properties; and the technical problems of poor antibacterial property of sutures, susceptibility to infection, and large suture resistance. The suture thread includes a suture thread body with a rough structure, and a first polymer material layer arranged on the surface of the suture thread body; the second lubricating liquid that can form a self-lubricating layer is stored in the molecular gap of the first polymer material layer. The titanium-nickel alloy material includes a titanium-nickel alloy substrate with a uniform porous structure on the surface; a polymer material layer is provided in the porous structure and on the surface of the titanium-nickel alloy substrate; the first layer of self-lubricating layer is stored between the molecular gaps of the polymer material layer. Two lubricants.

Description

Anti-adhesion antibacterial suture, anticoagulant antibacterial titanium-nickel alloy material and preparation method

technical field

The invention relates to a suture thread, a titanium-nickel alloy material used for human implantation materials and a preparation method thereof, in particular to an anti-adhesion antibacterial suture thread, an anticoagulation antibacterial titanium-nickel alloy material and a preparation method.

Background technique

During surgical operations, antibacterial is one of the first difficulties to be overcome. How to make the materials used in human body sustain antibacterial during operation is an important factor to evaluate the prognosis.

First, human implantation operations, such as artificial heart valves, artificial heart stents, etc. Although these implantable medical devices have saved the lives of countless patients, they also have serious defects, such as postoperative coagulation reactions and bacterial infections. Therefore, how to improve the anticoagulant and antibacterial properties of implanted medical materials is an urgent problem to be solved. question.

When the implant material is in contact with blood, the fibrin in the blood is first adsorbed on the surface of the implant material. On the one hand, the adsorbed fibrin further absorbs platelets, thereby activating platelets to form thrombus. On the other hand, the adsorbed fibrin activates the coagulation system in the body, promotes the release of coagulation factors, interacts with platelets to generate thrombin, and finally absorbs blood components to form thrombus. Therefore, reducing the adsorption of blood components such as fibrin on the surface of implant materials, thereby preventing the activation of the coagulation system, has become an effective method to improve anticoagulant performance. There are various strategies to reduce the adsorption of implant materials, such as surface passivation, heparin-containing anticoagulant coating, etc. Although these methods show good anticoagulant and antibacterial properties in the early stage, over time, these coatings Gradually depleting exposes a less biocompatible surface that loses anticoagulant and antimicrobial properties.

Secondly, during the use of surgical sutures, the metal sutures will adhere to the new tissue as the wound grows and heals, which will easily cause bleeding and damage to the healing tissue during the removal of the sutures. In addition, the infection during and after the operation of medical metal suture is also an important factor that threatens the life safety of patients.

The earliest artificial synthetic sutures are generally twisted or braided. The main problems are: on the one hand, due to the rough surface structure, the friction force is relatively large during suture, which is easy to cause large tissue drag deformation; Due to the capillary effect, it is easy to cause bacteria to hide in the groove structure on the surface of the suture, thus causing postoperative infection. Thus, in the 1970's, sutures in the form of monofilaments appeared on the market. The monofilament suture solves the problem of multiple strands to a certain extent due to its smoother surface. However, since the monofilament suture cannot be processed thicker, in order to prevent the problems of difficulty in bending and knotting. In recent years, people have developed barbed sutures on the basis of monofilament sutures. This kind of sutures does not need to be knotted, and the barbs on the surface of the sutures are used as fixed anchor points, which can effectively prevent the sutures from breaking. Relatively sliding, so as to achieve the purpose of fixing the wound. However, the barbed structure will not only reduce the tensile strength of the suture, but also increase the drag on the tissue during suturing, and its application range is limited to a certain extent.

Contents of the invention

The purpose of the present invention is to solve the problem of poor biocompatibility exposed during use in reducing the adsorption of implant materials, thereby losing anticoagulant and antibacterial properties; To solve the technical problem, an anti-adhesion antibacterial suture, an anticoagulant antibacterial titanium-nickel alloy material and a preparation method are proposed.

General idea of the present invention: Inspired by earthworms in nature that can crawl in moist soil and keep themselves clean, the present invention proposes a method for preparing a self-lubricating layer on a titanium-nickel alloy substrate.

Technical scheme of the present invention is:

An anti-adhesion antibacterial suture, which is special in that:

It includes a suture body whose surface is set as a rough structure, and a first polymer material layer arranged on the surface of the suture body;

A second lubricating liquid is stored in the molecular gap of the first polymer material layer, and the second lubricating liquid diffuses to the surface of the first polymer material layer to form a self-lubricating layer;

The first polymer material layer includes a first lubricating liquid and a first polymer material.

Further, the first polymer material is polydimethylsiloxane, and the first lubricating liquid is high-viscosity silicone oil;

The volume ratio of high-viscosity silicone oil to polydimethylsiloxane is (0.1-1.5):1, and the viscosity range of high-viscosity silicone oil is 100-500cps;

The second lubricating liquid is low-viscosity silicone oil, and the viscosity range of the low-viscosity silicone oil is 5-100 cps, and the viscosity of the low-viscosity silicone oil is lower than that of the high-viscosity silicone oil.

Further, the suture body is a second polymer material or a biological material or a metal material;

The second macromolecular material is polyethylene, polypropylene, polydioxanone or polylactic acid; the biological material is sheep casing, pig casing or ramie; the metal material is titanium-nickel alloy or stainless steel.

Further, the first polymer material layer is doped with anti-infective drugs.

Further, the suture body is a monofilament suture.

Further, the monofilament suture is provided with a pore structure inside.

Further, the pore density of the pore structure presents a stepped distribution along the radial direction of the suture, close to the axis of the monofilament suture, the pore density of the pore structure is low, far away from the axis of the monofilament suture, the pore structure high pore density.

Further, the monofilament suture is a second polymer material or a biological material;

The pore structure of the monofilament suture is filled with low-viscosity silicone oil, and the low-viscosity silicone oil seeps out to the surface of the first polymer material layer to form a self-lubricating layer.

Further, the suture body is a multi-strand braided suture.

Further, there is at least one functional filament in the multi-strand braided suture, and the functional filament has a pore structure inside.

Further, the multi-strand braided suture is a second polymer material or a biological material;

The functional silk has the same components as the first polymer material layer, which are high-viscosity silicone oil and polydimethylsiloxane;

The pore structure of the functional silk is filled with low-viscosity silicone oil, and the low-viscosity silicone oil seeps out to the surface of the first polymer material layer on the surface of the suture body to form a self-lubricating layer.

Further, the functional filament is located at the axis of the braided suture, and other filaments are braided around the circumferential surface of the functional filament.

The present invention also provides a kind of above-mentioned anti-adhesion antibacterial suture preparation method, and its special feature is that, comprises the following steps:

A1. Roughen the surface of the suture body to form a rough structure on the surface;

A2. Mix the first lubricating liquid and the first polymer material, and stir evenly to form a liquid gel of the first polymer material;

A3. Coating the surface of the suture body with a rough structure prepared in step A1 with the liquid first polymer material gel prepared in step A2, so that the liquid first polymer material gel evenly adheres to the surface of the suture body;

A4. The gel of the first polymer material in the liquid state is solidified, that is, the liquid becomes a gel-like substance, and the first polymer material layer is formed in the rough structure and on the surface of the suture body;

A5. Soak the suture in step A4 into the second lubricating solution, take it out after soaking for 30-50 hours, and dry it to obtain anti-adhesion and antibacterial suture.

Further, the first polymer material is polydimethylsiloxane; the first lubricating liquid is high-viscosity silicone oil; the volume ratio of high-viscosity silicone oil to polydimethylsiloxane is (0.1-1.5): 1. The viscosity range of high-viscosity silicone oil is 100-500cps;

The second lubricating liquid is low-viscosity silicone oil, and the viscosity range of the low-viscosity silicone oil is 5-100 cps, and the viscosity of the low-viscosity silicone oil is lower than that of the high-viscosity silicone oil.

The present invention also provides another anti-adhesion antibacterial suture, which is special in that:

It includes a suture body whose surface is set to a rough structure, the suture body is a monofilament type suture, the monofilament type suture is provided with a pore structure inside, the pore structure is filled with a second lubricating liquid, and the second lubricating liquid seeps out Form a self-lubricating layer on the surface of the suture body.

Further, the pore density of the pore structure presents a stepped distribution along the radial direction of the suture, close to the axis of the monofilament suture, the pore density of the pore structure is low, far away from the axis of the monofilament suture, the pore structure high pore density.

Further, the second lubricating liquid is low-viscosity silicone oil, and the viscosity range of the low-viscosity silicone oil is 5-100 cps.

The present invention also provides a third anti-adhesion antibacterial suture, which is special in that:

It includes a suture body whose surface is set to a rough structure, the suture body is a multi-strand braided suture, and the multi-strand braided suture includes at least one strand of functional silk and multi-strand fiber filaments, and the interior of the functional silk is provided with pores structure, the pore structure is filled with the second lubricating liquid, and the second lubricating liquid seeps to the surface of the suture body to form a self-lubricating layer.

Further, the second lubricating liquid is low-viscosity silicone oil, and the viscosity range of the low-viscosity silicone oil is 5-100 cps.

The functional silk includes high-viscosity silicone oil and polydimethylsiloxane, the volume ratio of high-viscosity silicone oil and polydimethylsiloxane is (0.1-1.5): 1; the viscosity range of high-viscosity silicone oil is 100～ 500cps, the viscosity of low-viscosity silicone oil is less than that of high-viscosity silicone oil.

Further, the functional filament is located at the axis of the braided suture, and other fiber filaments are braided around the circumferential surface of the functional filament.

The present invention also provides an anticoagulation and antibacterial titanium-nickel alloy material, which is special in that:

Including titanium-nickel alloy substrate;

The surface of the titanium-nickel alloy substrate has a uniform porous structure;

A polymer material layer is provided in the porous structure and on the surface of the titanium-nickel alloy matrix;

The polymer material layer is formed by mixing and solidifying the first lubricating liquid and the first polymer material;

A second lubricating liquid is stored between molecules of the polymer material layer, and the second lubricating liquid seeps out to the surface of the polymer material layer to form a self-lubricating layer.

Further, the first polymer material is polydimethylsiloxane, the first lubricating liquid is high-viscosity silicone oil, and the volume ratio of high-viscosity silicone oil to polydimethylsiloxane is, high-viscosity silicone oil: polydimethylsiloxane Methylsiloxane=(0.1～1.5):1, the viscosity range of the high viscosity silicone oil is 100～500cps;

The second lubricating liquid is low-viscosity silicone oil, and the viscosity range of the low-viscosity silicone oil is 5-100 cps, and the viscosity of the low-viscosity silicone oil is lower than that of the high-viscosity silicone oil.

The present invention also provides a method for preparing the above-mentioned anticoagulation and antibacterial titanium-nickel alloy material, which is special in that it includes the following steps:

S1. Using a femtosecond laser to prepare a porous structure on the surface of the titanium-nickel alloy substrate to obtain a porous titanium-nickel alloy substrate;

S2. According to the volume ratio, high-viscosity silicone oil: polymer material = (0.1-1.5): 1, measure high-viscosity silicone oil and polymer material, mix and stir to make a mixture of polymer material and high-viscosity silicone oil, and apply covered on the porous titanium-nickel alloy substrate; the viscosity range of the high-viscosity silicone oil is 100-500cps;

S3. After standing until the mixture of polymer material and high-viscosity silicone oil is evenly distributed on the surface of the porous titanium-nickel alloy substrate, place the porous titanium-nickel alloy substrate coated with the mixture of polymer material and high-viscosity silicone oil in a vacuum chamber. Vacuum until no bubbles are generated on the surface of the porous titanium-nickel alloy substrate;

The porous titanium-nickel alloy substrate coated with a mixture of polymer materials and high-viscosity silicone oil is exposed to ultraviolet light for 1-2 hours, and then heated to 75-85°C for curing, and the heating time is 1-2 hours to form polymers. material layer;

S4. After the porous titanium-nickel alloy substrate with a polymer material layer solidified on the surface is cooled naturally, the whole is immersed in low-viscosity silicone oil. The viscosity range of low-viscosity silicone oil is 5-100cps. After 30 to 50 hours, take it out and dry it to obtain an anticoagulant and antibacterial titanium-nickel alloy material.

Beneficial effects of the present invention:

1. The anti-adhesion and antibacterial suture provided by the present invention has a self-lubricating layer on the surface of the suture. Compared with the traditional untreated suture, the self-lubricating layer can make body fluids adsorb on the surface of the suture during use. , Inhibit the adhesion of cells and tissues, and improve the anti-adhesion effect of sutures.

2. The anti-adhesion and antibacterial suture provided by the present invention is made of lubricating oil-friendly material as a whole, which can store a large amount of lubricating liquid for continuous formation of a lubricating layer on the surface of the suture, and has long-term lubricity.

3. In the anti-adhesion antibacterial suture provided by the present invention, some drugs can also be doped in the self-lubricating layer for sterilization and anti-inflammation at the initial stage of implantation. The self-release of the drug and the self-lubricating and anti-adhesion properties of the self-lubricating layer are The antimicrobial properties of the suture provide protection.

4. The functional filament contained in the braided suture provided by the present invention can not only provide lubricating fluid, but also its material can be adjusted according to needs. For example, when high-strength polymer fiber material or stainless steel fiber material is used for weaving, it can be used A functional filament with low compressive strength is added to the center of the suture. When in use, the cross-section of the suture will be deformed when it is bent. This is mainly provided by the functional filament, which not only ensures the tensile strength of the suture, but also increases It improves the bending flexibility of the suture and makes the suture easier to use.

5. The surface of the suture provided by the present invention is coated with a layer of polymer material with self-lubricating properties, preferably polydimethylsiloxane gel material, which is close to the superficial tissue of the human body in physical properties It is easy to deform when squeezed, and restores its shape when there is no external force. This feature is just suitable for wound suture. Under the action of suture force, the surface of the suture is deformed, so that the position of the suture is relatively fixed and it is easy to sew. Knot; when the suture is removed, the suture force disappears, and the surface of the suture returns to be flat, so that it is easy to remove the suture, which will facilitate the actual application of the suture.

6. The titanium-nickel alloy material provided by the present invention is filled with polydimethylsiloxane gel in the three-dimensional micro-nano porous structure on the titanium-nickel alloy substrate to strengthen the polydimethylsiloxane gel and titanium-nickel alloy. The adhesion of the material makes the polydimethylsiloxane gel like a big tree rooted in the soil, and there is no problem of coating peeling off.

7. The preparation method of the anticoagulation and antibacterial titanium-nickel alloy material of the present invention constructs a three-dimensional porous structure on the surface of the titanium-nickel alloy by femtosecond laser, and then premixes high-viscosity silicone oil and polydimethylsiloxane to prepare polydimethylsiloxane Oxygen (S-PDMS) gel is coated on the porous surface, and finally the porous titanium-nickel alloy coated with S-PDMS gel is immersed in low-viscosity silicone oil, and the low-viscosity silicone oil will spontaneously ooze out on the surface of S-PDMS gel And form a lubricating layer, and finally form a self-lubricating layer on the titanium-nickel alloy.

8. S-PDMS is a straight-chain silicone oil before solidification, so it also has certain lubricity. Therefore, in use, even if the lubricating liquid layer mainly composed of low-viscosity silicone oil is completely consumed, the S-PDMS layer covered by the suture or the titanium-nickel alloy surface still has liquid repellency and lubricity, thereby prolonging the service life of the product .

9. The high-viscosity silicone oil in polydimethylsiloxane (S-PDMS) gel reduces the crosslinking degree of S-PDMS, so that the low molecular weight silicone oil can be stored in the gap of S-PDMS by soaking, which can be slowly Self-releasing for long-term self-lubrication.

10. The titanium-nickel alloy material prepared by the present invention has a self-lubricating layer, which can isolate the contact between the base material and body fluid, and reduce the adhesion of blood, bacteria and other components on the surface of the material, so as to solve the problem of heparin in the existing anticoagulant drug fixation method. Reduction of activity, pollution by chemical methods, and performance failure caused by the loss of lubricating fluid in the porous super-slippery surface of liquid perfusion. It has good anti-coagulation, anti-bacterial, anti-shedding, anti-corrosion and good stability, which can reduce The adhesion of 74% fibrin on the surface of titanium-nickel alloy can increase the corrosion resistance of simulated body fluids by 5448 times; even if the low-viscosity silicone oil adsorbed in the gap of S-PDMS is completely consumed, the liquid repellency of the surface will be slightly decreased, but still exists.

11. The preparation method of the present invention is safe and pollution-free, does not use any fluorine-containing substances, and meets the safety requirements of the human body.

Description of drawings

Fig. 1 is the process flow diagram of a kind of anti-adhesion antibacterial suture preparation method embodiment of the present invention;

Fig. 2 is a schematic diagram of the structure of a monofilament type suture in the anti-adhesion antibacterial suture embodiment of the present invention;

Fig. 3 is a structural schematic diagram of a braided suture in an anti-adhesion antibacterial suture embodiment of the present invention;

Fig. 4 is a schematic structural view of another monofilament type suture in the anti-adhesion antibacterial suture embodiment of the present invention;

Fig. 5 is a structural schematic diagram of another kind of braided suture in the anti-adhesion antibacterial suture embodiment of the present invention;

Figure 6 is a schematic diagram of anti-adhesion distribution in animal experiments of the embodiment of the present invention; wherein, (a) is the blank control group of untreated nickel-titanium alloy sutures, and (b) is the surface of untreated nickel-titanium alloy sutures after 3 weeks; ( c) is the untreated suture surface after 5 weeks, (d) is the suture blank control group with self-lubricating isolation layer, (e) is the suture surface with self-lubricating isolation layer after 3 weeks; (f) is The suture surface with self-lubricating isolation layer after 5 weeks; (g) is the fluorescence image of the untreated Nitinol suture blank control group, (h) is the fluorescence of the untreated Nitinol suture surface after 3 weeks Figure; (i) is the fluorescence image of the untreated suture surface after 5 weeks, (j) is the fluorescence image of the suture blank control group with self-lubricating isolation layer, (k) is the self-lubricating isolation layer after 3 weeks The fluorescence picture of the surface of the suture; (l) is the fluorescence picture of the surface of the suture with self-lubricating isolation layer after 5 weeks;

Fig. 7 is the flow chart of the embodiment of the preparation method of the anticoagulant antibacterial titanium-nickel alloy material of the present invention;

Fig. 8 is the structural cross-sectional view of each step of the titanium-nickel alloy material in the embodiment of the preparation method of the anticoagulant antibacterial titanium-nickel alloy material of the present invention;

Fig. 9 is the comparative schematic diagram of the contact state of the droplet on each test surface of the embodiment of the present invention; Wherein (a) is the PDMS surface, (b) is the surface of S-PDMS, (c) is the nickel-titanium with self-lubricating layer alloy surface;

Fig. 10 is a comparative schematic diagram of the sliding properties of droplets on various test surfaces according to the embodiment of the present invention; wherein, (a) is the surface of PDMS, (b) is the surface of S-PDMS, and (c) is a sliding surface with a self-lubricating layer Titanium-nickel alloy surface;

Fig. 11 is a comparative schematic diagram of the sliding properties of blood on various test surfaces according to the embodiment of the present invention; (a) is an untreated titanium-nickel alloy surface, and (b) is a titanium-nickel alloy surface with a self-lubricating layer;

Fig. 12 is a schematic diagram showing the comparison of fluorescence density of fluorescently labeled fibrin in an embodiment of the present invention on an untreated titanium-nickel alloy surface (I) and a titanium-nickel alloy surface (II) with a self-lubricating layer;

Figure 13 is a schematic diagram of the comparison of the fibrin concentration of fluorescently labeled fibrin on the untreated titanium-nickel alloy surface (I) and the titanium-nickel alloy surface (II) with a self-lubricating layer according to the embodiment of the present invention;

Fig. 14 is the schematic diagram of colony distribution on each test surface of E. coli culture experiment of the embodiment of the present invention; Wherein, (a) is blank control group, (b) is untreated titanium-nickel alloy surface, (c) has self-lubricating layer The surface of the titanium-nickel alloy; and the schematic diagram of the colony distribution on each test surface of the Staphylococcus aureus culture experiment; wherein, (d) is a blank control group, (e) is an untreated titanium-nickel alloy surface, and (f) is a self-lubricating layer of titanium-nickel alloy surface;

15 is a schematic diagram of the comparison of the anti-E. coli rate of the untreated titanium-nickel alloy surface (I) and the sliding titanium-nickel alloy surface (II) with a self-lubricating layer in the E. coli culture experiment of the embodiment of the present invention;

Figure 16 is a schematic diagram of the comparison of the anti-Staphylococcus aureus rate between the untreated titanium-nickel alloy surface (I) and the titanium-nickel alloy surface (II) with a self-lubricating layer in the Staphylococcus aureus culture experiment of the embodiment of the present invention;

Fig. 17 is the untreated titanium-nickel alloy surface (I-1) tested in the corrosion resistance test of the embodiment of the present invention, the fitted untreated titanium-nickel alloy surface (I-2), and the tested titanium-nickel alloy with self-lubricating layer Schematic diagram of the frequency-modulus comparison of the alloy surface (Ⅱ-1) and the fitted titanium-nickel alloy surface with a self-lubricating layer (Ⅱ-2);

Fig. 18 is the untreated titanium-nickel alloy surface (I-1) tested in the corrosion resistance test of the embodiment of the present invention, the fitted untreated titanium-nickel alloy surface (I-2), and the tested titanium-nickel alloy with self-lubricating layer Schematic diagram of the frequency-phase comparison of the alloy surface (Ⅱ-1) and the fitted titanium-nickel alloy surface with a self-lubricating layer (Ⅱ-2);

Fig. 19 is a schematic diagram of an equivalent circuit in a corrosion resistance test of an embodiment of the present invention;

Fig. 20 is a schematic diagram of comparison of equivalent resistance value results in the corrosion resistance test of the embodiment of the present invention;

Figure 21 is a schematic diagram of the self-repairing properties of the surface of the titanium-nickel alloy with a self-lubricating layer according to an embodiment of the present invention; wherein, (a) is a schematic diagram of the self-repairing principle, and (b) blood has a self-lubricating layer of titanium-nickel alloy after self-repairing Schematic diagram of alloy surface sliding test results;

Fig. 22 is the untreated titanium-nickel alloy surface (I) of the embodiment of the present invention, has the self-lubricating layer titanium-nickel alloy surface (II) and anticoagulant antibacterial titanium-nickel alloy material surface without low-viscosity silicone oil self-secretion state (Ⅲ) Schematic diagram of the measurement results of the viscous force of a water droplet.

The reference signs are as follows:

1-monofilament suture, 2-first polymer material layer, 3-self-lubricating layer, 4-porous structure, 5-low viscosity silicone oil, 10-multi-strand braided suture, 11-functional silk, 12- Fibrous filaments, 21-titanium-nickel alloy matrix, 22-porous structure, 23-polymer material layer.

Detailed ways

Example 1

A kind of anti-adhesion antibacterial suture as shown in Figure 2, this suture comprises monofilament type suture 1, and the surface of monofilament type suture 1 is set as rough structure; Covered with the first polymer material layer 2; the second lubricating liquid is stored between the molecular gaps of the first polymer material layer 2, and the second lubricating liquid seeps out and forms a self-lubricating fluid on the surface of the first polymer material layer 2 Layer 3; the second lubricating liquid is low-viscosity silicone oil 5, and the viscosity of low-viscosity silicone oil 5 is 5-100 cps, and the viscosity of low-viscosity silicone oil 5 is smaller than that of high-viscosity silicone oil.

The density of the pore structure 4 inside the monofilament suture 1 presents a stepped distribution along the radial direction of the suture, and the pore structure 4 is a tapered hole whose diameter gradually decreases toward the axial direction of the monofilament suture 1. The closer to the axis of the monofilament suture 1 , the lower the density of the pore structure 4 is. This structure can make the monofilament suture 1 not only have higher tensile strength, but also have good bending flexibility, which is more convenient for suturing in operation.

The pore structure 4 of the monofilament suture 1 is filled with the second lubricating liquid, and the second lubricating liquid seeps out to the surface of the suture body to form a self-lubricating layer 3 . The self-lubricating layer 3 ensures that the suture will not have muscle tissue adhesion during use, which facilitates the removal of the suture when the wound is healing. The second lubricating liquid is low-viscosity silicone oil 5, and the viscosity range of low-viscosity silicone oil 5 is 5-100 cps.

The first polymer material layer 2 is a polydimethylsiloxane gel material, and the polydimethylsiloxane gel is made of high-viscosity silicone oil and polydimethylsiloxane in a volume ratio of (0.3-1.5 ): 1 mixed and then solidified, and the viscosity of the high-viscosity silicone oil is 100-500cps; preferably, the viscosity of the high-viscosity silicone oil is 100-200cps, and the mixing volume ratio of the high-viscosity silicone oil and polydimethylsiloxane is set to (1.0～1.5):1; the viscosity of high-viscosity silicone oil is 200-400cps, the mixing volume ratio of high-viscosity silicone oil and polydimethylsiloxane is set to (0.7-1.0):1; the viscosity of high-viscosity silicone oil is 400-500cps , The mixing volume ratio of high-viscosity silicone oil and polydimethylsiloxane is set to (0.3-0.7):1. Preferably, anti-infective drug components are also added in the first polymer material layer 2, which can further prevent bacterial infection. For example, if the drug containing silver ions is added, the silver ions will be released slowly. When the silver ions contact the pathogenic bacteria , will lead to the demise of pathogenic bacteria, so as to achieve the purpose of anti-infection.

In other embodiments, the first polymer material layer 2 can also be other polymer silicone gels, or hydrogels such as acrylamide hydrogel, polyvinyl alcohol hydrogel or cellulose hydrogel, which are all The pro-lubricating liquid material can absorb and store the second lubricating liquid in the molecular gap; wherein, the first lubricating liquid and the second lubricating liquid in the hydrogel are both deionized water, and the deionized water stored in the molecular gap of the hydrogel After oozing out, a self-lubricating layer3 will be formed on the surface of the hydrogel.

Since polydimethylsiloxane gel is a pro-lubricant material, a large amount of low-viscosity silicone oil 5 can be stored in the gap of the polydimethylsiloxane gel layer, which can ensure that the low-viscosity silicone oil 5 leaks out of polydimethylsiloxane The surface of the silicone gel layer forms a self-lubricating layer3. In actual use, when the content of low-viscosity silicone oil 5 reaches the storage capacity of polydimethylsiloxane PDMS, the low-viscosity silicone oil 5 adsorbed in the gap of the polydimethylsiloxane gel layer will spontaneously ooze out, A layer of self-lubricating layer 3 is formed on the surface of the monofilament suture 1 body, and the self-lubricating layer 3 will absorb the low-viscosity silicone oil 5 stored in the polydimethylsiloxane gel layer; until the low-viscosity silicone oil 5 is lower than The lowest adsorption concentration, low-viscosity silicone oil 5 can not be released, but because the polydimethylsiloxane gel S-PDMS is a straight-chain silicone oil before solidification, it also has a certain lubricity, so in use, Even if the self-lubricating layer 3 based on low-viscosity silicone oil 5 is completely consumed, the polydimethylsiloxane gel layer covered on the surface of the monofilament suture 1 body still has liquid repellency and lubricity, thereby prolonging the suture. Service life of monofilament type sutures1.

When the monofilament suture 1 is used to suture a wound, the surface of the suture has a self-lubricating liquid, and the friction force is small, which can reduce dragging and deformation of human tissues, and is easy to suture; the self-lubricating liquid can also prevent bacterial infection; when After the wound is healed, the suture is removed, and it is easy to pull out because of the small friction force. It can be seen that the suture has multiple advantages.

In practical applications, the monofilament suture 1 can use one of the second polymer material, biological material, and metal material. The second polymer material can be polyethylene, polypropylene, polydioxanone, polylactobionic acid, etc.; the biological material can be sheep casing, pig casing, ramie, etc.; the metal material can be titanium-nickel alloy, stainless steel, etc. . The rough structure on the surface of the monofilament suture 1 is processed by laser. In this embodiment, femtosecond laser processing is used, and the rough structure on the surface is finer.

When the monofilament suture 1 is the second polymer material or biological material, the monofilament suture 1 is provided with a pore structure 4 inside, and the pore structure 4 is filled with a low-viscosity silicone oil 5, and the low-viscosity silicone oil 5 can be supplemented The low-viscosity silicone oil 5 carried by the suture surface coating prolongs the service life of the self-lubricating layer 3 .

It can be understood that the suture may also be a braided suture 10 of multi-strand braided type. As shown in FIG. , there is a rough structure on the surface of the weaving structure of the fiber filament 12, and the first polymer material layer 2 is coated on the surface of the rough structure and the weaving structure; low viscosity is stored between the molecular gaps of the first polymer material layer 2 Silicone oil 5, and the low-viscosity silicone oil 5 seeps out and forms a self-lubricating layer 3 on the surface of the first polymer material layer 2. Because monofilament sutures cannot be made thicker, otherwise, bending and knotting are more difficult, and braided sutures 10 just make up for this shortcoming, which not only has high tensile strength, but also has good bending flexibility sex.

When the braided suture 10 is the second polymer material or biological material, there is at least one functional filament 11 in the braided suture 10, and low-viscosity silicone oil 5 is stored inside the functional filament. Preferably, the functional silk 11 has a pore structure 4, and the interior of the pore structure 4 is filled with low-viscosity silicone oil 5; for example, the functional silk 11 with a sponge-like structure can store more low-viscosity silicone oil 5, greatly extending the suture The service life of the self-lubricating layer 3; the functional silk 11 can also be prepared from the first polymer material and high-viscosity silicone oil, and low-viscosity silicone oil 5 is stored between the molecular gaps of the functional silk 11, and the gap between the functional silk 11 is low. The viscous silicone oil 5 can self-seep to the surface of the first polymer material layer 2 on the surface of the braided suture 10 to form a self-lubricating layer 3 . The functional filament 11 is located at the center of the braided suture 10 , and other filaments are braided around the peripheral surface of the functional filament 11 .

Based on the above-mentioned anti-adhesion antibacterial suture, the present invention also provides its preparation method, which specifically includes the following steps:

Step 1, roughening the surface of the suture body to form a rough structure on the surface;

In this embodiment, sandpaper is used to polish the surface of the suture body to make the surface highly rough. In other embodiments, roughening techniques such as chemical etching or laser ablation can also be used. In laser ablation, energy can be used The 100-3000μJ laser is ablated on the surface of the suture body to form a uniformly distributed rough structure.

Step 2. Mix the high-viscosity silicone oil and polydimethylsiloxane at a volume ratio of (0.3-1.5): 1, and stir evenly to form a liquid polydimethylsiloxane gel;

Among them, the viscosity range of high-viscosity silicone oil is 100-500cps, and the viscosity selection of high-viscosity silicone oil is related to the dosage ratio of high-viscosity silicone oil; preferably, when the viscosity selection of high-viscosity silicone oil is low, the preparation of polydimethylsiloxane The volume of high-viscosity silicone oil will be relatively large when oxane gel (S-PDMS) is used. Similarly, when the viscosity of high-viscosity silicone oil is selected to be higher, the high viscosity when preparing polydimethylsiloxane gel (S-PDMS) The volume of silicone oil will be relatively small; for example, when the viscosity of high-viscosity silicone oil is 100cps, the volume ratio of high-viscosity silicone oil to polydimethylsiloxane (PDMS) is (1.2 ~ 1.5): 1, the effect will be better, and When the viscosity of the high-viscosity silicone oil is 500cps, the volume ratio of the high-viscosity silicone oil and polydimethylsiloxane (PDMS) is (0.1-0.5): 1, and the effect will be better; when the viscosity of the high-viscosity silicone oil is greater than 500cps, If the viscosity is too high, it is difficult to stir and mix when preparing polydimethylsiloxane gel (S-PDMS). At the same time, when high-viscosity silicone oil and polydimethylsiloxane (PDMS) are mixed in proportion, anti-infective drugs can also be added to improve the antibacterial performance of sutures.

Step 3: Coating the surface of the suture body with a rough structure prepared in step 1 with the liquid polydimethylsiloxane gel prepared in step 2, so that the liquid polydimethylsiloxane gel evenly adheres to the The surface of the suture body; at this time, the liquid polydimethylsiloxane gel (S-PDMS) will penetrate into the interior of the rough structure, and use the rough structure on the surface of the suture body to coat the polydimethylsiloxane gel Layers adhere firmly.

Step 4. After the liquid polydimethylsiloxane gel solidifies, that is, the liquid turns into a gel-like substance, and a polydimethylsiloxane gel layer is formed in the rough structure and on the surface of the suture body. Among them, the curing process can be selected to be heated and cured, and can also be selected to stand for curing. In order to save time, this embodiment chooses to heat and cure the liquid polydimethylsiloxane gel (S-PDMS) to form polydimethylsiloxane. Oxygen gel layer. If it is a metal substrate, it needs to be assisted by ultraviolet light while heating.

Step 5. Infiltrate the low-viscosity silicone oil 5 with a viscosity of 5 to 100 cps into the gap of the polydimethylsiloxane gel layer. The viscosity of the low-viscosity silicone oil 5 is lower than that of the high-viscosity silicone oil. In this embodiment, it will be treated in step 4 The suture body is soaked in the low-viscosity silicone oil 5 with a viscosity ranging from 5 to 100 cps. In other embodiments, the surface of the suture body treated in step 4 can also be coated with the low-viscosity silicone oil 5 with a viscosity of 5 to 100 cps. ; Make the low viscosity silicone oil 5 penetrate into the gap of the polydimethylsiloxane gel layer, take it out after soaking for 30-50 hours and dry it, the low viscosity silicone oil 5 will reversely penetrate into the polydimethylsiloxane gel layer On the surface, a self-lubricating isolation layer is formed, and anti-adhesion and antibacterial sutures are prepared.

The characteristics of the anti-adhesion antibacterial suture are further illustrated through relevant tests below.

Through animal experiments, as shown in Figure 6, the untreated sutures were placed in the mouse heart for incubation, and were taken out after three and five weeks. In the third week, it was found that there were some network structures distributed on the untreated surface, and in the fifth There is a layer of tissue growing on the peripheral surface, and the anti-adhesion antibacterial suture of the present invention has nothing on the surface of the anti-adhesion antibacterial suture due to the existence of the self-lubricating isolation layer, showing good anti-tissue adhesion (fluorescent figure, untreated There are some white flocs on the surface in the third and fifth weeks. These white flocs are new tissues, indicating that there is adhesion of the suture; the surface of the suture treated with the self-lubricating layer provided by this example does not appear white flocs symptoms, indicating that there is no new tissue growth, that is, no adhesions.).

Through the bacterial culture test, as shown in Figure 12, the Escherichia coli and Staphylococcus aureus on the surface of the untreated suture and the surface of the anti-adhesion antibacterial suture with a self-lubricating isolation layer were compared and found that the self-lubricating isolation layer provided by this embodiment The anti-adhesion antibacterial suture surface of the layer has obvious antibacterial properties, and the antibacterial rate against Escherichia coli and Staphylococcus aureus both reaches more than 98%.

The invention provides a self-lubricating isolation layer on the surface of the suture to inhibit the adhesion of cells, tissues and bacteria on the surface of the suture, thereby improving the anti-adhesion and antibacterial properties of the medical suture.

Example 2

An anti-adhesion antibacterial suture as shown in Figure 4, comprising a suture body with a rough structure on the surface, the suture body is a monofilament suture 1, and the monofilament suture 1 is internally provided with a pore structure 4, the pores The structure 4 is filled with the second lubricating liquid, and the second lubricating liquid seeps out to the surface of the suture main body to form a self-lubricating layer 3 . The self-lubricating layer 3 ensures that the suture will not have muscle tissue adhesion during use, which facilitates the removal of the suture when the wound is healing. The second lubricating liquid is low-viscosity silicone oil 5, and the viscosity range of the silicone oil is 5-100 cps. When the interior has a pore structure 4, the suture has better flexibility and is easy to bend and knot. Its longitudinal stretchability will also be improved, so that it is more suitable for the changes of swelling and detumescence of the sutured wound.

The density of the pore structure 4 inside the monofilament suture 1 presents a stepped distribution along the radial direction of the suture, and the closer to the axis of the monofilament suture 1 , the lower the density of the pore structure 4 . This structure can make the monofilament suture 1 not only have higher tensile strength, but also have good bending flexibility, which is more convenient for suturing in operation.

Example 3

An anti-adhesion and antibacterial suture as shown in Figure 5, including a suture body, the suture body is a multi-strand braided suture 10, at least one of the multi-strand braided sutures 10 is a functional filament 11 And the multi-strand fiber filaments 12, the inside of the functional filament 11 is provided with a pore structure 4, the inside of the pore structure 4 is filled with a second lubricating liquid, and the second lubricating liquid seeps out to the surface of the suture body to form a self-lubricating layer 3, the self-lubricating layer 3. It ensures that the suture will not have muscle tissue adhesion during use, which is convenient for removing the suture during wound healing; the lubricating fluid is low-viscosity silicone oil 5, and the viscosity range of silicone oil is 5-100cps; the compressive strength of functional silk 11 is lower than Fiber filaments 12 of other strands. In this way, when the suture is bent and folded during use, the cross-section of the functional filament 11 is easier to deform, which improves the bending flexibility of the suture.

Preferably, the functional silk 11 has the same composition as the first polymer material layer, the first polymer material layer includes high-viscosity silicone oil and polydimethylsiloxane, and the volume ratio of high-viscosity silicone oil and polydimethylsiloxane is , high-viscosity silicone oil: polydimethylsiloxane ﹦ (0.1～1.5): 1, the viscosity of high-viscosity silicone oil is greater than or equal to 100cps and less than or equal to 500cps, low-viscosity silicone oil is stored between the molecular gaps of functional silk 11, Low viscosity silicone oils are less viscous than high viscosity silicone oils. The low-viscosity silicone oil will penetrate to the surface of the suture to form a self-lubricating layer 3 .

Preferably, the functional filament 11 is located at the axis of the braided suture 10 , and other filaments are braided around the circumferential surface of the functional filament 11 .

Example 4

The present embodiment provides an anticoagulant and antibacterial titanium-nickel alloy material, as shown in Fig. 8, the material includes a titanium-nickel alloy substrate 21, and the titanium-nickel alloy material has the advantages of corrosion resistance, superelasticity, and good biocompatibility; titanium-nickel alloy The surface of the substrate 21 has a uniform porous structure 22; the polymer material layer is formed in the porous structure 22 and the surface of the titanium-nickel alloy substrate 21; the polymer material layer is formed by curing polydimethylsiloxane gel; Silicone gel includes high-viscosity silicone oil and polydimethylsiloxane, the volume ratio of high-viscosity silicone oil and polydimethylsiloxane is, high-viscosity silicone oil:polydimethylsiloxane﹦(0.1～1.5 ): 1. The viscosity of the high-viscosity silicone oil is greater than or equal to 100cps and less than or equal to 500cps. Preferably, the viscosity of the high-viscosity silicone oil is 100-200cps, and the mixing volume ratio of the high-viscosity silicone oil and polydimethylsiloxane is set to (1.2-1.5 ): 1; the viscosity of high-viscosity silicone oil is 200-400cps, and the mixing volume ratio of high-viscosity silicone oil and polydimethylsiloxane is set to (0.5-1.2): 1; the viscosity of high-viscosity silicone oil is 400-500cps, and the high-viscosity silicone oil The mixing volume ratio with polydimethylsiloxane is set to (0.1-0.5):1. The polydimethylsiloxane gel gap stores low-viscosity silicone oil 5, the viscosity of the low-viscosity silicone oil 5 is 5-100 cps, and the viscosity of the low-viscosity silicone oil 5 is smaller than that of the high-viscosity silicone oil. A large amount of low-viscosity silicone oil 5 can be stored in the gap of the polydimethylsiloxane gel layer, which can ensure that the low-viscosity silicone oil 5 seeps out of the surface of the polydimethylsiloxane gel layer to form a self-lubricating layer 3 .

It can be understood that the polymer material layer can also be other polymer silicone gels, or hydrogels such as acrylamide hydrogel, polyvinyl alcohol hydrogel or cellulose hydrogel, which are all pro-lubricating liquid materials , the second lubricating liquid can be absorbed and stored in the molecular gap; wherein, the first lubricating liquid and the second lubricating liquid in the hydrogel are both deionized water, and the deionized water stored in the molecular gap of the hydrogel will ooze out A self-lubricating layer 3 is formed on the surface of the hydrogel.

Referring to Fig. 7, this embodiment also provides a method for preparing the above-mentioned anticoagulant antibacterial titanium-nickel alloy material, the method comprising the following steps:

S1. Using a femtosecond laser to prepare a porous structure 22 on the surface of the titanium-nickel alloy substrate 21, the porous titanium-nickel alloy substrate; specifically, the femtosecond laser generates a femtosecond pulse laser, the femtosecond pulse laser has a wavelength of 1030nm and a pulse width 400fs-10ps, the red light output frequency is 25KHz-5MHz, and then through Thorlabs, AX-250, the axicon lens with a cone angle α of 1° is spatially shaped into a conical light field distribution of the Bessel profile; the output of the axicon The conical light field of the Bessel profile is collimated by the first lens to form a parallel laser beam, which is then focused on the surface of the titanium-nickel alloy material through the micromachining system; A reflector behind the lens, a shutter and a magnifying objective lens; the magnification of the magnifying objective lens is ×20, and NA=0.40. The femtosecond laser beam focused on the surface of the titanium-nickel alloy material processes a uniformly distributed porous structure 22 on the surface of the titanium-nickel alloy material through a three-dimensional machining movement. The laser can choose FemtoYL-40, YSLP laser, or others; in this embodiment, the parameters of the laser setting are: the frequency is set to 2500KHz, the frequency is selected by the signal generator at 2KHz, the rising edge is triggered, and the duty cycle is 20% , the power is 2170mW, the scanning speed is 12000μm/s, and the scanning interval is 6μm.

S2. According to the volume ratio, high-viscosity silicone oil: polydimethylsiloxane = (0.1-1.5): 1, measure high-viscosity silicone oil and polydimethylsiloxane, stir to make polydimethylsiloxane A mixture of alkane and high-viscosity silicone oil, and coated on the porous titanium-nickel alloy substrate; wherein, the viscosity of the high-viscosity silicone oil is greater than or equal to 100cps and less than or equal to 500cps. The amount ratio is relevant. Preferably, when the viscosity of high-viscosity silicone oil is selected to be low, the volume of high-viscosity silicone oil is relatively large when preparing a mixed solution of polydimethylsiloxane and high-viscosity silicone oil. Similarly, high-viscosity silicone oil When the viscosity is selected higher, the volume of the high-viscosity silicone oil is relatively small when preparing the mixed solution of polydimethylsiloxane and high-viscosity silicone oil. Specifically, when the viscosity of the first silicone oil is 100-200cps, the first silicone oil and high-viscosity silicone oil It will be better if the mixing volume ratio of polydimethylsiloxane (PDMS) is set to (1.2-1.5):1; when the viscosity of the first silicone oil is 200-400cps, the first silicone oil and polydimethylsiloxane (PDMS) mixing volume ratio is set to (0.5 ~ 1.2): 1 better; and when the viscosity of the first silicone oil is 400 ~ 500cps, the mixing volume of the first silicone oil and polydimethylsiloxane (PDMS) If the ratio is set to (0.1～0.5):1, the effect will be better; when the viscosity of the first silicone oil is greater than 500cps, the viscosity is too high, it is difficult to stir and mix when preparing the polydimethylsiloxane mixed solution, and after curing The polymer layer has poor toughness and is easily damaged.

The doping of high-viscosity silicone oil and PDMS not only reduces the degree of cross-linking of PDMS, but also makes high-viscosity silicone oil stored inside the PDMS cross-linking network. However, the surface is still composed of PDMS hydrophobic ends and high-viscosity silicone oil molecules, so it still has a certain liquid repellency. When the content of low-viscosity silicone oil increases until it exceeds the storage capacity of PDMS, the low-viscosity silicone oil self-releases to form a lubricating layer on the surface, which has stronger liquid repellency.

S3, let it stand until the mixed solution of polydimethylsiloxane and high-viscosity silicone oil is evenly distributed on the surface of the porous titanium-nickel alloy substrate, and then the porous layer coated with the mixed solution of polydimethylsiloxane and high-viscosity silicone oil The titanium-nickel alloy substrate is placed in a vacuum chamber, and the vacuum is evacuated until no bubbles are generated on the surface of the porous titanium-nickel alloy substrate. The gas in the mixed solution of polydimethylsiloxane and high-viscosity silicone oil is removed by vacuuming to further improve the performance of polydimethylsiloxane. Properties of the mixture of methyl siloxane and high-viscosity silicone oil; heat the mixture of polydimethylsiloxane and high-viscosity silicone oil to 75-85°C, and cure it under heating for 1-2 hours to form polydimethylsiloxane Silicone gel layer;

S4. After the porous titanium-nickel alloy substrate with the polydimethylsiloxane gel layer solidified on the surface is cooled naturally, immerse it in low-viscosity silicone oil 5 with a viscosity of 5-100 cps, soak it for 30-50 hours, take it out and wipe it dry. Obtain the anticoagulant antibacterial titanium-nickel alloy material, the surface of the anticoagulant antibacterial titanium-nickel alloy material will ooze out low-viscosity silicone oil 5 to form a self-lubricating layer 3. The release forms a lubricating layer on the surface of the titanium-nickel alloy substrate 21, which has strong liquid repellency; when the content of the low-viscosity silicone oil 5 is lower than the storage capacity of PDMS, the low-viscosity silicone oil 5 cannot self-release, but the high-viscosity silicone oil and The doping of PDMS not only reduces the degree of cross-linking of PDMS, but also makes the high-viscosity silicone oil stored in the PDMS cross-linking network. Viscosity silicone oil molecular composition, so it still has a certain liquid repellency.

The characteristics of the anticoagulant and antibacterial titanium-nickel alloy materials are further illustrated below through relevant tests.

As shown in Figures 9 to 11, compared with the titanium-nickel alloy without self-lubricating layer, when the droplet slides on the surface of the titanium-nickel alloy with the self-lubricating layer 3, the droplet is separated from the surface of the titanium-nickel alloy by the self-lubricating layer. Open, reducing the adsorption of titanium-nickel alloy to droplets;

As shown in Figure 12-Figure 13, the use of blood containing fluorescently labeled fibrin has verified that the titanium-nickel alloy with the self-lubricating layer 3 can pass through the blood quickly (0.18s), and the titanium-nickel alloy with the self-lubricating layer has only a small amount of blood Adsorption (fluorescence density 13%, fibrin concentration 0.309mg/mL), while blood on the surface of the untreated titanium-nickel alloy passed slowly (2.48s) and was mostly adsorbed on the surface of the untreated titanium-nickel alloy (fluorescence density 51%, fibrin concentration Concentration 0.843mg/mL).

As shown in Figures 14-16, through bacterial culture tests, Escherichia coli and Staphylococcus aureus on the surface of the untreated titanium-nickel alloy and the surface of the titanium-nickel alloy with a self-lubricating layer are compared and found that the self-lubricating The performance of the titanium-nickel alloy of the layer has obvious antibacterial properties, and the antibacterial rate against Escherichia coli can reach 98.29%, and the antibacterial rate against Staphylococcus aureus can reach 99.7%.

As shown in Figures 17 to 20, the electrochemical workstation is used to perform electrochemical corrosion in a simulated body fluid environment on the surface of the titanium-nickel alloy with a self-lubricating layer and the surface of the untreated titanium-nickel alloy. Figure 17 is the Nyquist modulus diagram of the sample under simulated body fluid corrosion. The larger the modulus value, the greater the impedance value in the simulated body fluid and the stronger the corrosion resistance. The results show that the titanium-nickel alloy with a self-lubricating layer Compared with the untreated titanium-nickel alloy, the corrosion resistance is improved by 10 ⁷ orders of magnitude. Figure 18 is the Nyquist phase diagram of the sample under simulated body fluid corrosion; the titanium-nickel alloy with a self-lubricating layer has two peaks, indicating that there are two coatings for inhibiting body fluid corrosion; the untreated titanium-nickel alloy has only one peak , indicating that there is only one layer of anti-corrosion coating, which is the oxide film on the surface, and the phase diagram shows that the self-lubricating surface has an additional layer of protection compared to the intrinsic surface, which is the surface oxide film and self-lubricating layer. Figure 19 is an equivalent circuit diagram of the corrosion resistance of the titanium-nickel alloy surface with a self-lubricating layer, R _s represents the impedance of the simulated body fluid, R _f represents the coating resistance, and R _ct represents the charge transfer between the coating and the nickel-titanium alloy substrate of impedance. Fig. 20 shows the specific values of each impedance, which shows that the corrosion resistance of the surface of the titanium-nickel alloy with a self-lubricating layer has been greatly improved.

As shown in Figure 21, when the self-lubricating layer on the surface is damaged, the low-viscosity silicone oil 5 stored inside can spontaneously flow to the damaged part to restore the lubricating layer on the surface and restore its original liquid repellency. Figure 21(a) is a schematic diagram of the principle of self-repair, and Figure 21(b) is the surface slippery test of blood after self-repair (put it aside for half an hour after being scratched with a knife, and the white dotted line is the damaged position of the knife scratch), indicating that there is The surface recovery effect of the self-lubricating layer of titanium-nickel alloy is good.

As shown in Figure 22, in the process of peeling off the water droplets from the untreated Ti-Ni alloy surface, a part of the water droplets adhered to the untreated Ti-Ni alloy surface showed high viscosity, while the water droplets on the Ti-Ni alloy with a self-lubricating layer When the surface is peeled off, it is completely desorbed, showing the low adhesion of the self-lubricating surface; when the low-viscosity silicone oil 5 content is lower than the storage capacity of PDMS, the low-viscosity silicone oil 5 cannot self-release and form a self-lubricating layer on the surface of the titanium-nickel alloy. force, which is higher than the viscous force of the Ti-Ni alloy surface with a self-lubricating layer, but lower than that of the untreated Ti-Ni alloy surface, indicating that with the consumption of the lubricating fluid, even if the surface lubricating fluid disappears completely, it also presents a Some liquid repellency and anti-adhesion, but the anti-adhesion performance will be slightly reduced.

Claims (23)

1. An anti-adhesion antibacterial suture line, which is characterized in that:

the suture line comprises a suture line body with a rough structure arranged on the surface and a first polymer material layer (2) arranged on the surface of the suture line body;

a second lubricating liquid is stored in the molecular gap of the first polymer material layer (2), and the second lubricating liquid is diffused to the surface of the first polymer material layer (2) to form a self-lubricating layer (3);

the first polymer material layer (2) comprises a first lubricating liquid and a first polymer material.

2. The anti-adhesion antimicrobial suture of claim 1, characterized in that:

the first polymer material is polydimethylsiloxane, and the first lubricating liquid is high-viscosity silicone oil;

the volume ratio of the high-viscosity silicone oil to the polydimethylsiloxane is (0.1-1.5): 1, the viscosity range of the high-viscosity silicone oil is 100-500 cps;

the second lubricating fluid is low-viscosity silicone oil (5), the viscosity range of the low-viscosity silicone oil (5) is 5-100 cps, and the viscosity of the low-viscosity silicone oil (5) is smaller than that of the high-viscosity silicone oil.

3. The anti-adhesion antimicrobial suture of claim 2, characterized in that:

the suture line body is made of a second polymer material or a biological material or a metal material;

the second high molecular material is polyethylene, polypropylene, polydioxanone or poly lactobionic acid; the biological material is sheep casing, pig casing or ramie; the metal material is titanium-nickel alloy or stainless steel.

4. The anti-adhesion antimicrobial suture of claim 3, characterized in that:

the first polymer material layer (2) is doped with anti-infective drugs.

5. The anti-adhesion antibacterial suture according to any one of claims 1 to 4, wherein:

the suture body is a monofilament type suture (1).

6. The anti-adhesion antimicrobial suture of claim 5, characterized in that: a pore structure (4) is arranged inside the monofilament type suture (1).

7. The anti-adhesion antimicrobial suture of claim 6, wherein: the pore density of the pore structure (4) is distributed in a step shape along the radial direction of the suture line, is close to the axis of the monofilament suture line (1), is low in pore density of the pore structure (4), is far away from the axis of the monofilament suture line (1), and is high in pore density of the pore structure (4).

8. The anti-adhesion antimicrobial suture of claim 7, wherein:

the monofilament suture (1) is made of a second high polymer material or a biological material;

and the pore structure (4) of the monofilament suture line (1) is filled with low-viscosity silicone oil (5), and the low-viscosity silicone oil (5) seeps out to the surface of the first polymer material layer (2) to form the self-lubricating layer (3).

9. The anti-adhesion antimicrobial suture of any one of claims 1 to 4, wherein:

the suture body is a multi-strand woven suture (10).

10. The anti-adhesion antimicrobial suture according to claim 9, wherein:

the multi-strand woven suture (10) is provided with at least one functional yarn (11) and a plurality of fiber yarns (12), and the functional yarn (11) is internally provided with a pore structure (4).

11. The anti-adhesion antimicrobial suture of claim 10, wherein:

the multi-strand woven suture (10) is made of a second high polymer material or a biological material;

the functional yarn (11) and the first polymer material layer (2) have the same components and are high-viscosity silicone oil and polydimethylsiloxane;

the pore structure (4) of the functional silk (11) is filled with low-viscosity silicone oil (5), and the low-viscosity silicone oil (5) seeps out of the surface of the first polymer material layer (2) on the surface of the suture line body to form a self-lubricating layer (3).

12. The anti-adhesion antimicrobial suture of claim 11, wherein:

the functional yarn (11) is positioned at the axle center of the multi-strand woven suture (10), and the fiber yarn (12) is woven around the circumferential surface of the functional yarn (11).

13. A method for preparing an anti-adhesion antibacterial suture according to any one of claims 1 to 12, comprising the steps of:

a1, roughening the surface of a suture body to form a rough structure on the surface;

a2, mixing the first lubricating liquid and the first high polymer material, and uniformly stirring to form liquid first high polymer material gel;

a3, coating the liquid first high polymer material gel prepared in the step A2 on the surface of the suture line body with the rough structure prepared in the step A1, so that the liquid first high polymer material gel is uniformly adhered to the surface of the suture line body;

a4, curing the liquid first polymer material gel, namely changing the liquid into a colloidal substance, and forming a first polymer material layer (2) in the rough structure and on the surface of the suture line body;

and A5, soaking the suture thread obtained in the step A4 into a second lubricating liquid for 30-50 hours, taking out and drying to obtain the anti-adhesion antibacterial suture thread.

14. The method of preparing an anti-adhesion antimicrobial suture according to claim 13, wherein:

the first high polymer material is polydimethylsiloxane; the first lubricating liquid is high-viscosity silicone oil; the volume ratio of the high-viscosity silicone oil to the polydimethylsiloxane is (0.1-1.5): 1; the viscosity range of the high-viscosity silicone oil is 100-500 cps;

the second lubricating fluid is low-viscosity silicone oil (5), the viscosity range of the low-viscosity silicone oil (5) is 5-100 cps, and the viscosity of the low-viscosity silicone oil (5) is less than that of the high-viscosity silicone oil.

15. An anti-adhesion antibacterial suture line, which is characterized in that:

the novel self-lubricating suture line comprises a suture line body with a rough structure arranged on the surface, wherein the suture line body is a monofilament suture line (1), a pore structure (4) is arranged inside the monofilament suture line (1), second lubricating liquid is filled in the pore structure (4), and the second lubricating liquid seeps out to the surface of the suture line body to form a self-lubricating layer (3).

16. The anti-adhesion antimicrobial suture of claim 15, wherein:

the pore density of the pore structure (4) is distributed in a step shape along the radial direction of the suture line, is close to the axis of the monofilament suture line (1), is low in pore density of the pore structure (4), is far away from the axis of the monofilament suture line (1), and is high in pore density of the pore structure (4).

17. The anti-adhesion antimicrobial suture of claim 15 or 16, wherein:

the second lubricating fluid is low-viscosity silicone oil (5), and the viscosity range of the low-viscosity silicone oil (5) is 5-100 cps.

18. An anti-adhesion antibacterial suture line is characterized in that:

the novel woven suture line comprises a suture line body with a rough structure arranged on the surface, wherein the suture line body is a multi-strand woven suture line (10), the multi-strand woven suture line (10) comprises at least one strand of functional yarn (11) and a plurality of strands of fiber yarns (12), a pore structure (4) is arranged inside the functional yarn (11), a second lubricating liquid is filled inside the pore structure (4), and the second lubricating liquid seeps out to the surface of the suture line body to form a self-lubricating layer (3).

19. The anti-adhesion antimicrobial suture of claim 18, wherein:

the second lubricating fluid is low-viscosity silicone oil (5), and the viscosity range of the low-viscosity silicone oil (5) is 5-100 cps.

The functional silk (11) comprises high-viscosity silicone oil and polydimethylsiloxane, and the volume ratio of the high-viscosity silicone oil to the polydimethylsiloxane is (0.1-1.5): 1; the viscosity range of the high-viscosity silicone oil is 100-500 cps, and the viscosity of the low-viscosity silicone oil (5) is less than that of the high-viscosity silicone oil.

20. The anti-adhesion antimicrobial suture of claim 18 or 19, wherein:

the functional yarn (11) is positioned at the axle center of the multi-strand woven suture (10), and the fiber yarn (12) is woven around the circumferential surface of the functional yarn (11).

21. An anticoagulant antibacterial titanium-nickel alloy material is characterized in that:

comprises a titanium-nickel alloy matrix (21);

the surface of the titanium-nickel alloy matrix (21) is provided with a uniform porous structure (22);

a polymer material layer (23) is arranged in the porous structure (22) and on the surface of the titanium-nickel alloy matrix (21);

the polymer material layer (23) is formed by mixing and solidifying a first lubricating liquid and a first polymer material;

and a second lubricating liquid is stored between the molecular gaps of the polymer material layer (23), and the second lubricating liquid seeps out to the surface of the polymer material layer (23) to form a self-lubricating layer (3).

22. The anticoagulant antibacterial titanium-nickel alloy material according to claim 21, characterized in that:

the first high polymer material is polydimethylsiloxane, the first lubricating liquid is high-viscosity silicone oil, and the volume ratio of the high-viscosity silicone oil to the polydimethylsiloxane is as follows: polydimethylsiloxane = (0.1-1.5): 1, wherein the viscosity range of the high-viscosity silicone oil is 100-500 cps;

the second lubricating fluid is low-viscosity silicone oil (5), the viscosity range of the low-viscosity silicone oil (5) is 5-100 cps, and the viscosity of the low-viscosity silicone oil (5) is smaller than that of the high-viscosity silicone oil.

23. A method for preparing the anticoagulant antibacterial titanium-nickel alloy material according to claim 21 or 22, which is characterized by comprising the following steps:

s1, preparing a porous structure (22) on the surface of a titanium-nickel alloy matrix (21) by adopting a femtosecond laser to obtain a porous titanium-nickel alloy matrix;

s2, according to the volume ratio, high-viscosity silicone oil: 1, measuring high-viscosity silicone oil and a high-molecular material, mixing and stirring to prepare a mixed solution of the high-molecular material and the high-viscosity silicone oil, and coating the mixed solution on the porous titanium-nickel alloy substrate; the viscosity range of the high-viscosity silicone oil is 100-500 cps;

s3, standing until the mixed solution of the high molecular material and the high viscosity silicone oil is uniformly distributed on the surface of the porous titanium-nickel alloy matrix, placing the porous titanium-nickel alloy matrix coated with the mixed solution of the high molecular material and the high viscosity silicone oil in a vacuum chamber, and vacuumizing until no bubbles are generated on the surface of the porous titanium-nickel alloy matrix;

irradiating the porous titanium-nickel alloy matrix coated with the mixed solution of the high polymer material and the high-viscosity silicone oil by ultraviolet light for 1-2 hours, and then or simultaneously heating to 75-85 ℃ for curing, wherein the heating time is 1-2 hours, so as to form a high polymer material layer (23);

s4, after the porous titanium-nickel alloy matrix with the polymer material layer (23) solidified on the surface is naturally cooled, the whole body is immersed in low-viscosity silicone oil (5), the viscosity range of the low-viscosity silicone oil (5) is 5-100 cps, the viscosity of the low-viscosity silicone oil (5) is smaller than that of the high-viscosity silicone oil, the porous titanium-nickel alloy matrix is taken out after being immersed for 30-50 hours and then wiped to dry, and the anticoagulant antibacterial titanium-nickel alloy material is obtained.

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