Homogeneous coated fiber material based on electrostatic-air jet coaxial spinning and preparation method thereof

Abstract

The present invention discloses a homogeneous coating fiber material based on electrostatic-jet coaxial spinning and a preparation method thereof, wherein the homogeneous coating fiber material based on electrostatic-jet coaxial spinning includes a core layer located inside and a cortex layer arranged outside the core layer; the material of the core layer includes at least one of degradable polyurethane (BPU) and degradable polyester (BPE); the material of the cortex layer includes a water-soluble polymer matrix, a functional compound molecule, and a cross-linking agent; the functional compound molecule includes at least one compound molecule of anticoagulation, anticalcification, antioxidation, antiproliferation, and anti-infection. The present invention adopts homogeneous blending technology to prepare a spinning solution, and then spins a uniform skin-core structure fiber through a special electrostatic-jet coaxial spinning nozzle, and then soaks in a dilute solution of a green cross-linking agent, ultrasonically washes, pre-freezes, and vacuum freeze-dries to obtain a highly efficient functionalized fiber of the finely controlled coating.

Description

Technical Field

[0001] The present invention relates to the technical field of preparing high-efficiency functionalized fibers by using a homogeneous and precisely controlled coating technology, and in particular to a homogeneous coating fiber material based on electrostatic-air jet coaxial spinning and a preparation method thereof. Background Art

[0002] Biofunctional fiber materials are widely used in clinical device-related products in the cardiovascular field. Among them, devices that come into contact with blood, such as cardiovascular and cerebrovascular stents, artificial valves, artificial blood vessels, heart occluders, ventricular assist devices, etc., are faced with problems such as bleeding, infection, thrombosis, hyperplasia, and calcification; especially artificial vascular devices, which have a large contact area with blood and activate the original homeostasis of blood after transplantation to cause coagulation or hemolysis. At the same time, as exogenous foreign bodies, these devices are also very easy to cause infection. Therefore, they face great challenges in terms of blood compatibility, and long-term application is greatly restricted, and may even lead to the death of patients. At present, in terms of improving the blood compatibility, antibacterial properties, and cell compatibility of medical devices, the main focus is on functional modification of the surface / interface of device materials, hoping to reduce the adverse reactions in the early stage of medical device implantation and reduce the complications of long-term application. However, the effectiveness and long-term effectiveness of existing functional coating technologies cannot meet the requirements of existing device implantation.

[0003] The fiber materials prepared by electrospinning technology have controllable mechanical properties, are easy to shape, and can be functionally modified. They can be used as base materials for artificial blood vessels, cardiovascular stent coatings, heart valves, heart occluders and other devices, but related device products still face problems such as blood compatibility. Taking small-caliber artificial blood vessels as an example, they can be used for peripheral vascular replacement, heart bypass, arteriovenous fistula establishment and other surgeries. Despite its broad application prospects, such products have not yet been commercialized due to the limitations of functional technical defects such as anticoagulation and anticalcification of fiber materials. Materials such as polyester and polytetrafluoroethylene have been widely used in the research and development and production of large-caliber artificial blood vessels, and have achieved certain results, but the five-year patency rate of the above products is only about 39%, and it is even more unrealistic to use them in small-caliber vascular transplantation. Therefore, it is particularly urgent to carry out long-term functional modification of artificial vascular materials. At present, surface modification, coating technology and physical hybridization technology are commonly used modification technologies. There are many disadvantages of hybridization through physical mixing, such as uneven mixing of components, which affects the mechanical properties of the device and the active release characteristics of the hybrid components.

[0004] The disadvantage of chemical modification is that it can easily lead to the degradation of the scaffold material, affecting its bulk performance. In addition, the harsh reaction conditions, such as high temperature, can easily lead to the inactivation of active molecules, and can also be accompanied by side reactions that bring biological toxicity. The effect of physical coating is unstable, and it is difficult for the coating to be effectively attached to the interface. Therefore, the precise preparation of fiber coatings through coaxial electrospinning technology is of great significance in the field of medical devices and their materials. Summary of the invention

[0005] The problem to be solved by the present invention is to provide a uniform coated fiber material based on electrostatic-jet coaxial spinning and a preparation method thereof; the present invention prepares high-efficiency functionalized fibers based on the uniform and precisely controlled coating technology of jet-coaxial electrospinning, so as to overcome the defects of the existing functional coating technology in the anti-coagulation, anti-calcification, antibacterial and other effects after the functionalization transformation of biomedical fiber materials.

[0006] The uniform coated fiber material based on electrostatic-jet coaxial spinning provided by the present invention comprises an inner core layer, the core layer component is a biomedical polymer material with adjustable mechanics and molecular weight; a cortex layer arranged outside the core layer, the cortex layer is prepared from a water-soluble polymer matrix with excellent biocompatibility, functional compound molecules uniformly distributed in the matrix, and a green cross-linking agent.

[0007] The core layer and the skin layer are coaxial structures. The uniform coating fiber material based on electrostatic-jet coaxial spinning is prepared by a water-soluble polymer matrix / functional compound molecules / green cross-linking agent blend with excellent biocompatibility as the skin layer material and high-quality biomedical polymers as the core layer material through a solution coaxial spinning method.

[0008] The purpose of the present invention is specifically achieved through the following technical solutions:

[0009] First aspect:

[0010] The present invention provides a uniform coated fiber material based on electrostatic-air jet coaxial spinning, wherein the uniform coated fiber material based on electrostatic-air jet coaxial spinning comprises a core layer located inside and a skin layer arranged around the outside of the core layer;

[0011] The material of the core layer includes at least one of degradable polyurethane (BPU) and degradable polyester (BPE);

[0012] The material of the cortex includes a water-soluble polymer matrix, functional compound molecules, and a cross-linking agent;

[0013] The functional compound molecules include at least one compound molecule of anticoagulation, anticalcification, antioxidation, antiproliferation and anti-infection.

[0014] The functional compound molecule is heparin.

[0015] The water-soluble polymer matrix is ​​polyethylene oxide (PEO) with a weight average molecular weight of 400,000 to 600,000 and / or polyvinyl alcohol (PVA) with a weight average molecular weight of 80,000 to 200,000.

[0016] The mass ratio of the functional compound molecules to the water-soluble polymer matrix is ​​0.1:100 to 10:100.

[0017] The mass ratio of the cross-linking agent to the functional compound molecules is 0.1:10 to 0.1:1.

[0018] The ratio of the core layer diameter to the bioactive functional fiber diameter is 1:25 to 1:100.

[0019] The cross-linking agent is a green cross-linking agent.

[0020] The green cross-linking agent includes at least one of proanthocyanidins, curcumin, tannic acid, catechol, gallic acid, and chlorogenic acid.

[0021] Second aspect:

[0022] The present invention also provides a method for preparing a uniform coated fiber material based on electrostatic-air jet coaxial spinning, comprising the following steps:

[0023] S1. Preparation of core layer solution: dissolving the material for preparing the core layer in a solvent to prepare a core layer solution;

[0024] S2. Preparation of cortical solution: blending a water-soluble polymer matrix, a functional compound molecule, and a dispersant, and stirring the mixture to obtain a cortical solution;

[0025] S3, electrostatic-jet coaxial spinning: On the electrostatic spinning device, the core layer solution and the skin layer solution are respectively placed in the propeller, the skin layer solution propulsion speed is 0.6-1.5mL / h, the core layer propulsion speed is 0.8-1.2mL / h, the air flow velocity at the nozzle is in the range of 20-110m / s, and then respectively propelled and metered by the propulsion pump, and then the spinning needle is pressurized with direct current, and the aluminum receiving device receives the ejected fiber to obtain the skin-core structure primary fiber;

[0026] S4, fiber post-treatment: the skin-core structured primary fiber obtained in step S3 is immediately immersed in a dilute solution of a crosslinking agent (a green crosslinking agent can be used as the crosslinking agent); the skin-core structured fiber after immersion is washed with water, and then pre-frozen and vacuum freeze-dried to obtain the uniform coated fiber material based on electrostatic-jet coaxial spinning.

[0027] The present invention found that only by strictly controlling the concentration of the core layer spinning solution, the concentration of the skin layer solution, the skin layer solution advancement speed, the core layer advancement speed, and the air flow speed at the nozzle, can a functional fiber scaffold with uniform skin-core structure, controllable skin and core layer thickness, and uniform fiber diameter distribution be stably spun.

[0028] In step S1, the concentration (w / v) of the core layer solution is 6% to 20%;

[0029] In step S2, the concentration (w / v) of the cortical solution is 0.5% to 5%.

[0030] More preferably, the propeller in step S2 is a 10 mL syringe, the distance between the needle tip and the receiving device is 8 to 20 cm, the DC voltage at the needle tip is 6 to 20 kV, and the device for receiving the fiber is one of aluminum foil and a 316L stainless steel rod coated with a super lubricant.

[0031] More preferably, the green crosslinking agent dilute solution in S4 is one of the ethanol solutions of proanthocyanidins, curcumin, tannic acid, catechol, gallic acid, and chlorogenic acid, and the concentration of the solution (solute mass: solvent volume) is 0.1% to 3.5%. The obtained functional fiber scaffold can maintain high biosafety and high-efficiency anticoagulation, anticalcification, antibacterial and other effects.

[0032] More preferably, the pre-freezing temperature in step S4 is -80 to -20°C for 24 to 72 hours, and the vacuum freeze drying temperature is -120 to -96°C for 24 to 72 hours. This ensures that the obtained functional fiber scaffold will not collapse and has the same morphology as the initial design, so that the mechanical compliance can be guaranteed during use.

[0033] Preferably, the spinning nozzle of the electrospinning device is an electrostatic-air-jet coaxial needle.

[0034] The third aspect

[0035] The present invention also provides a high-efficiency functional fiber based on the electrostatic-air jet combined coaxial electrospinning uniform precision controlled coating technology for use in the preparation of fiber-based clinical instrument products in the cardiovascular field.

[0036] The key point of the present invention is that the coaxial needle used is an electrostatic-jet coaxial needle with controllable spinning speed; it is electrostatic-jet coaxial, rather than the common electrospinning coaxial needle or the jet needle for melt-blown spinning commonly used in the prior art; the fiber spun by the common coaxial needle, the fiber functionalized by conventional chemical impregnation, and the fiber demolded by a general non-super-lubricating mold are compared and found that only the homogeneous, precisely controlled coating and efficient functionalized fiber described in the present application by solution electrostatic-jet coaxial spinning can achieve efficient anti-coagulation, anti-calcification, antibacterial and other effects, because:

[0037] 1) Only the efficient functionalized fibers prepared by the coaxial electrospinning homogeneous and precisely controlled coating technology combined with solution electrostatic-air jet have uniform fiber structure and stable three-dimensional structure of biomimetic extracellular matrix;

[0038] 2) Only when the mass ratio of functional compound molecules to water-soluble polymer matrix is ​​controlled to be 0.1:100-10:100, the mass ratio of green crosslinker to functional compound molecules is controlled to be 0.1:10-0.1:1 during the preparation process; and the ratio of core layer diameter to fiber diameter in bioactive functional fibers is 1:25-1:100, can a functional fiber scaffold with uniform morphology, stable structure, good biocompatibility, no hypersensitivity reaction to the human body during transplantation surgery, and affinity with blood and surrounding tissues in the human body be obtained;

[0039] 3) Only by using the homogeneous blending technology to prepare the spinning solution, and then spinning the skin-core structure fiber with uniform morphology through the electrostatic-jet coaxial spinning nozzle, and then soaking in a dilute solution of green crosslinking agent, ultrasonic washing, pre-freezing, and vacuum freeze-drying, can we obtain high-efficiency functional fibers with precisely controlled coatings; and the functional compound molecules evenly distributed in the fiber cortex have a clear release cycle and are evenly distributed on the fiber surface, which has anti-coagulation, anti-calcification, antibacterial and other effects.

[0040] The beneficial effects of the present invention are:

[0041] 1. The present invention provides a method for preparing a high-efficiency functionalized fiber for cardiovascular device products with a uniform coating; the long-lasting functionalized fiber is prepared based on the solution electrostatic-air jet combined coaxial electrospinning uniform precision coating technology, and the fiber core layer is a high-quality biomedical polymer component with clear components and a clear degradation cycle, which plays a mechanical support role;

[0042] 2. The cortex is mainly composed of three components: water-soluble polymer matrix / functional compound molecules / green cross-linking agent. The functional compound molecules evenly distributed in the cortex have a clear release cycle and are evenly distributed on the fiber surface, playing an anti-coagulation, anti-calcification, antibacterial and other effects.

[0043] 3. Its preparation process is simple and efficient, with uniform morphology, stable structure, and good biocompatibility. It has no hypersensitivity reaction to the human body during transplantation surgery. At the same time, it has affinity with the blood and surrounding tissues in the human body and is suitable for the treatment of cardiovascular and cerebrovascular diseases. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments made with reference to the following drawings:

[0045] Figure 1 Schematic diagram of functional fiber spinning using solution electrostatic-air jet coaxial needle;

[0046] Figure 2Schematic diagram of the cross section of the high-efficiency functionalized fiber prepared by the present invention, wherein 1 is the core layer, 2 is the water-soluble polymer matrix / functional compound molecule / green cross-linking agent blend, 3 is the water-soluble polymer matrix, and 4 is the functional compound molecule;

[0047] Figure 3 It is a schematic diagram of the structure of the electrostatic-air jet coaxial needle used in the present invention;

[0048] Figure 4 This is a transmission electron microscope image of the high-efficiency anticoagulant fiber coated with heparin prepared in the present invention;

[0049] Figure 5 The fiber samples are homogeneous and precisely controlled coated fibers prepared by the present invention, wherein B is a fiber membrane for heparinized heart valves with a homogeneous and precisely controlled coating, and A is a 6 mm caliber artificial blood vessel with heparin and a homogeneous and precisely controlled coating. DETAILED DESCRIPTION

[0050] The present invention is described in detail below in conjunction with embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, some adjustments and improvements can also be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0051] In order to make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0052] The invention provides a uniform coating fiber material based on electrostatic-air jet coaxial spinning. The fiber material comprises a core layer located inside and a skin layer arranged around the outside of the core layer.

[0053] Figure 1 Schematic diagram of functional fiber spinning using solution electrostatic-air jet coaxial needle;

[0054] Figure 2 Schematic diagram of the cross section of the high-efficiency functionalized fiber prepared by the present invention, wherein 1 is the core layer, 2 is the water-soluble polymer matrix / functional compound molecule / green cross-linking agent blend, 3 is the water-soluble polymer matrix, and 4 is the functional compound molecule;

[0055] Figure 3 Schematic diagram of the structure of the electrostatic-air jet coaxial needle used in the present invention; the electrostatic-air jet coaxial needle comprises a core material outlet and a skin material outlet surrounding the core material outlet, forming a coaxial structure;

[0056] The nozzle of the propulsion pump used in the following embodiments and comparative examples of the present invention has a plurality of jet holes; the needle is installed on the nozzle to form an electrostatic-jet coaxial structure.

[0057] Example 1

[0058] 1. Preparation of core layer solution: Prepare a solution with a weight average molecular weight of 1.0×10 5 The degradable polyester PLCL was dissolved in hexafluoroisopropanol, and the solution was magnetically stirred until it was clear, thereby preparing a PLCL solution with a concentration (w / v) of 10%;

[0059] 2. Preparation of cortical solution: tannic acid, heparin, and PEO with a weight average molecular weight of 400,000 are prepared in an aqueous solution at a mass ratio of 0.1:10:10000; the solution is magnetically stirred until it is clear, and a cortical spinning solution with a concentration (w / v) of 0.5% is prepared;

[0060] 3. The core layer solution and the skin layer solution were respectively filled into 10 mL syringes, and the advancement speed of the skin layer solution was set to 0.6 mL / h and the advancement speed of the core layer solution was set to 0.8 mL / h on the electrospinning device. The air flow velocity at the nozzle was in the range of 20 m / s, and then the advancement and metering were respectively carried out by the advancement pump, and then the spinning needle was pressurized to 15 kV by direct current, the spinning temperature was 25 ° C, the ambient humidity was set to 20%, and the flat aluminum receiving device received the ejected fiber to obtain the skin-core structured primary fiber;

[0061] 4. Immediately immerse the primary fibers of the skin-core structure in a 0.1% (w / v) tannic acid ethanol solution; immerse for 30 minutes, then ultrasonically wash for 5 minutes, pre-freeze at -80°C for 24 hours, and immediately vacuum freeze (-96°C) and dry for 24 hours to obtain the fiber membrane for heparinized heart valves with the uniform and precisely controlled coating.

[0062] The fiber membrane for heparinized heart valve prepared by this embodiment is as follows: Figure 5 As shown in B, the fiber membrane maintains good mechanical properties. B is a fiber membrane for heparinized heart valve with a uniform and precise coating, and A is a 6mm diameter heparin artificial blood vessel with a uniform and precise coating.

[0063] Example 2

[0064] 1. Preparation of core layer solution: Prepare a core layer solution with a weight average molecular weight of 9.5×10 4 The degradable polyurethane PEUU is dissolved in tetrahydrofuran, and the solution is magnetically stirred until it becomes clear, thereby preparing a PEUU solution with a concentration (w / v) of 10%;

[0065] 2. Preparation of cortical solution: prepare an aqueous solution with a concentration (w / v) of 3.5% by mass ratio of proanthocyanidins, heparin and PVA with a weight average molecular weight of 200,000 according to 0.1:1:10, stir the solution magnetically until it is clear, and prepare the cortical spinning solution;

[0066] 3. The prepared core layer solution and skin layer solution were respectively filled into 10mL syringes, and the advancement speeds of the skin layer solution and the core layer solution were set to 1.5mL / h and 1.2mL / h on the electrospinning device, respectively. The air flow velocity at the nozzle was in the range of 110m / s, and then they were pushed and metered by the propulsion pump, and then the spinning needle was pressurized to 15kV by direct current. The spinning temperature was 25℃, the ambient humidity was set to 20%, and the 316L stainless steel rod receiving device with a diameter of 6mm and coated with PTFE received the ejected fibers to obtain primary fibers with skin-core structure.

[0067] 4. Then, the obtained skin-core structured primary fiber is immediately immersed in a 1% proanthocyanidin ethanol solution; immersed for 10 minutes, then ultrasonically washed for 5 minutes, pre-frozen at -20°C for 72 hours, and immediately vacuum frozen (-120°C) and dried for 72 hours to obtain the heparin artificial blood vessel with the homogeneous and precisely controlled coating. Figure 5 As shown in A, the artificial blood vessel has a uniform appearance.

[0068] The fiber membrane for heparinized heart valve prepared by this embodiment is as follows: Figure 4 As shown, the fiber diaphragm maintains good mechanical properties.

[0069] Comparative Example 1

[0070] The difference between this comparative example and Example 2 is that the weight average molecular weight in the core layer solution is 1.0×10 5 The biodegradable polyester PLCL and the solvent hexafluoroisopropanol were replaced with a weight average molecular weight of 9.5×10 4 The biodegradable polyurethane PEUU and tetrahydrofuran were added, and the spinning parameters and post-treatment parameters were changed.

[0071] Comparative Example 2

[0072] The difference between this comparative example and Example 1 is that the cortical solution is different, as follows:

[0073] Preparation of cortical solution: Tannic acid, heparin, and PEO with a weight average molecular weight of 400,000 are prepared into a 2% aqueous solution at a mass ratio of 0.1:10:10000, and the solution is magnetically stirred until it is clear to prepare the cortical spinning solution.

[0074] Comparative Example 3

[0075] The difference between this comparative example and Example 1 is that heparin is replaced by warfarin.

[0076] Comparative Example 4

[0077] The difference between this comparative example and Example 1 is that when the concentration (w / v) of the skin spinning solution is adjusted from 0.5% to 6%, stable spinning cannot be achieved.

[0078] Comparative Example 5

[0079] The difference between this comparative example and Example 1 is that after the concentration (w / v) of the green crosslinking agent dilute solution is adjusted from 0.1% to 4% for post-treatment, the spun primary fiber does not have a stable skin-core structure and the ratio between the core layer diameter and the fiber diameter is not within the range of 1:25 to 1:100.

[0080] Comparative Example 6

[0081] The difference between this comparative example and Example 2 is that in step S3 of the preparation method, the solution advancement speed in the cortex is 1.6 mL / h, and the core layer advancement speed is 1.3 mL / h. The spun fiber presents a sheath-core structure and the ratio between the core layer diameter and the fiber diameter is not in the range of 1:25 to 1:100.

[0082] Comparative Example 7

[0083] The difference between this comparative example and Example 1 is that in step S3 of the preparation method, the air flow velocity at the nozzle is 120 m / s, the spun fiber presents a skin-core structure, and the ratio of the core layer diameter to the fiber diameter is not in the range of 1:25 to 1:100.

[0084] Comparative Example 8

[0085] The difference between this comparative example and Example 2 is that the preparation method uses a 316L stainless steel rod receiving device without PTFE coating to receive the ejected fibers, and the fiber tube spun on the 316L stainless steel rod cannot be completely demoulded.

[0086] Performance Testing

[0087] The heparin release cycle test, platelet adhesion density test and endothelial coverage test were respectively conducted on each embodiment and comparative example.

[0088] 1. Heparin release cycle test

[0089] Test method: Immerse 2g of heparin-loaded fiber scaffold in 2mL of PBS solution and place it in a shaker in a 37℃ constant temperature water bath for sustained release. Take out all 2mL of PBS solution at 12 hours, 1, 3, 5, 7, 10 and 14 days, and add an equal volume of new PBS solution. Mix the taken PBS solution with 2mL of toluidine blue solution (0.04wt% toluidine blue, 0.01NHCl, 0.2wt% NaCl), shake gently for 4h, then centrifuge at 1000r / m for 10min, rinse with PBS solution 1-2 times, and then dissolve in 5mL of a mixed solution of anhydrous ethanol and 0.1N NaOH. Use an ultraviolet spectrophotometer to test its absorbance value at 530nm to determine the amount of heparin in the solution.

[0090] 2. Platelet adhesion density test

[0091] Test method: Blood was drawn from the ear vein of healthy New Zealand white rabbits in a plastic vacuum tube (2.7 mL, Becton Dickinson, USA) containing 3.2% sodium citrate solution at a ratio of 9:1 (v / v). Platelet-rich blood (PRP, containing 2×10 per ml) was obtained by centrifugation at 1200 rpm for 10 minutes. 7 Platelet adhesion test steps are as follows: a 14 mm diameter circular nanofiber membrane is soaked in 75% ethanol for 15 minutes to clean and sterilize, then washed several times with deionized water, placed in a 24-well cell culture plate, 500 μL PRP is added to each well, and slowly shaken for 2 hours at 37°C, and then gently washed 10 times with PBS buffer solution to ensure that the non-adherent blood components are washed away. Then the sample is immersed in a 4% paraformaldehyde solution, fixed at 4°C for 2 hours, and dehydrated by gradient ethanol solution (30%, 50%, 70%, 80%, 90%, 95%, 100%), soaking for 15 minutes each time. The dehydrated sample is evaporated in a fume hood and then sprayed with gold, and the adhesion of platelets on the membrane surface is observed by scanning electron microscopy. In addition, the lactate dehydrogenase (LDH) kit (LDH, Clontech Laboratories) is used to quantitatively test the platelet adhesion.

[0092] 3. Endothelial coverage test

[0093] Test method: Take HUVECs cell suspension at 1.0×10 5The cells were directly planted in a 24-well plate at a planting amount of 100 cells / well. Before planting cells, each well on the 24-well plate was stacked with a special 316L stainless steel bar to divide the well into two parts. The area where the steel bar was stacked was the area where the cells could migrate and spread. After 12 hours, the cells to be planted had adhered to the sample membrane. The stacked steel bar was carefully removed and cultured for 48 hours. After 48 hours, the cell migration was measured. The specific steps were as follows: 4% paraformaldehyde was used to fix the cells in the well plate for more than 4 hours, PBS was washed for more than 3 times, 0.1% Triton X-100 was permeabilized for 20 minutes, and then rhodamine-labeled phalloidin and DAPI dye were added, and dyed for 15 minutes respectively. Finally, the migration distance of the stained cell nucleus compared with the original state was observed under an inverted fluorescence microscope and a scanning electron microscope, and the cell coverage percentage was calculated based on the SEM photos using Image J software. The endothelial coverage percentage was calculated as follows: C = cell coverage area / original area of ​​the well plate × 100%.

[0094] The results are shown in Table 1.

[0095] Table 1

[0096]

[0097] As shown in Table 1 or Figure 4 It can be seen that only by strictly following the configuration parameters of the spinning solution in the invention content, strictly following the spinning parameters and post-processing parameters, and through the electrostatic-jet coaxial spinning needle, can the skin-core structure fiber with uniform morphology be spun. After soaking in a dilute solution of a green crosslinker, ultrasonic washing, pre-freezing, and vacuum freeze-drying, efficient functionalized fibers with precisely controlled coatings can be obtained. Moreover, the functional compound molecules evenly distributed in the fiber cortex have a long release cycle, obvious anti-platelet adhesion performance, and efficient and rapid promotion of endothelial cell coverage.

[0098] By comparing and analyzing the sustained release period, anti-platelet adhesion ability and endothelial rapid coverage ability test results of the samples prepared in Examples 1 and 2 and Comparative Examples 1-8, it can be seen that the high-efficiency functionalized fiber with uniform and precisely controlled coating based on solution electrostatic-jet coaxial spinning, which is spun in strict accordance with the configuration parameters of the spinning solution in the content of the invention, and strictly following the spinning parameters and post-processing parameters, can achieve a maximum release period of 6.3 days for heparin, and the platelet adhesion amount can be controlled at a minimum of 504 / mm 2 The coverage rate of epithelial cells after culture can be as high as 81% within 48 hours.

[0099] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A uniform coated fiber material based on electrostatic-air jet coaxial spinning, characterized in that: The uniform coating fiber material based on electrostatic-air jet coaxial spinning comprises a core layer located inside and a skin layer arranged around the outside of the core layer; The material of the core layer includes at least one of degradable polyurethane BPU and degradable polyester BPE; The material of the cortex includes a water-soluble polymer matrix, functional compound molecules, and a cross-linking agent; The water-soluble polymer matrix is ​​polyethylene oxide PEO with a weight average molecular weight of 400,000 to 600,000 and / or polyvinyl alcohol PVA with a weight average molecular weight of 80,000 to 200,000; the mass ratio of the functional compound molecule to the water-soluble polymer matrix is ​​0.1:100 to 10:100; The functional compound molecule is heparin; The preparation method of the homogeneous coated fiber material based on electrostatic-air jet coaxial spinning comprises the following steps: S1. Preparation of core layer solution: dissolving the material for preparing the core layer in a solvent to prepare a core layer solution; the concentration w / v of the core layer solution is 6%~20%; S2. Preparation of cortical solution: blending the water-soluble polymer matrix and the functional compound molecules, stirring them evenly to prepare a cortical solution; the concentration w / v of the cortical solution is 0.5%~5%; S3, electrostatic-jet coaxial spinning: On the electrostatic spinning device, the core layer solution and the skin layer solution are respectively placed in the propeller, the skin layer solution propulsion speed is 0.6~1.5mL / h, the core layer propulsion speed is 0.8~1.2mL / h, the air flow velocity at the nozzle ranges from 20~110m / s, and then respectively propulsion and metering are carried out by the propulsion pump, and then the spinning needle is pressurized with direct current, and the receiving device receives the ejected fiber to obtain the skin-core structure primary fiber; wherein, the direct current voltage at the needle is 6~20kV; S4, fiber post-treatment: soaking the primary fiber with the core-skin structure obtained in step S3 in a dilute solution of a crosslinking agent; washing the soaked fiber with the core-skin structure with water, pre-freezing it, and vacuum freeze-drying it to obtain the uniform coated fiber material based on electrostatic-jet coaxial spinning; The cross-linking agent dilute solution is one of ethanol solutions of proanthocyanidins, curcumin, tannic acid, catechol, gallic acid and chlorogenic acid, and the mass concentration of the solution is 0.1% to 3.5%.

2. The uniform coated fiber material based on electrostatic-air jet coaxial spinning according to claim 1, characterized in that: The mass ratio of the cross-linking agent to the functional compound molecules is 0.1:10 to 0.1:

1.

3. The preparation method according to claim 1, characterized in that: In step S1, the material of the core layer includes at least one of degradable polyurethane BPU and degradable polyester BPE.

4. The preparation method according to claim 1, characterized in that: In step S4, the pre-freezing temperature is -80 to -20°C for 24 to 72 hours, and the vacuum freeze-drying temperature is -120 to -96°C for 24 to 72 hours.

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