Adhesive hydrogel fiber composite membrane adapted to dynamic organ mechanical properties, preparation method and application thereof

Abstract

The present invention provides an adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs, and a preparation method and application thereof, relating to the technical field of medical biomaterials. The adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs provided by the present invention comprises a micron fiber network scaffold layer, an electrospun nanofiber membrane layer deposited on both side surfaces and in a pore structure of the micron fiber network scaffold layer, and at least the electrospun nanofiber membrane layer on one side of the micron fiber network scaffold layer is loaded with porous self-gelling powder. After the "sandwich" structure hydrogel fiber composite membrane provided by the present invention contacts biological tissue and absorbs interfacial water, it quickly gels in situ to form a hydrogel layer, achieving strong tissue adhesion, while the micron fiber scaffold in the middle layer maintains mechanical strength and nonlinear mechanical elasticity. The hydrogel fiber composite membrane provided by the present invention can simultaneously meet the requirements of strong adhesion to wet tissue and biomechanical properties adapted to dynamic organs.

Description

Technical Field

[0001] The present invention relates to the technical field of medical biomaterials, and in particular to an adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs, and a preparation method and application thereof. Background Art

[0002] Current tissue adhesives, generally in liquid or wet gel state, rely mainly on the diffusion of their molecules (such as monomers, macromolecules or polymers) through interfacial water to form covalent / non-covalent bonds with the polymer network of the tissue. The strong adhesion properties of tissue adhesives in the wet gel state mainly depend on the balance between the hydrogel cohesion and the interfacial bonding strength. Improving adhesion performance often comes at the expense of hydrogel cohesion (mechanical properties), and vice versa. Although many bioadhesive hydrogels have been reported, these materials generally exhibit considerable mechanical differences compared to natural tissues. It remains a major challenge for hydrogel adhesives to meet the mechanical properties required for specific applications, such as adapting to dynamic organs, while maintaining strong adhesion to the target tissue. Summary of the Invention

[0003] In view of this, the present invention aims to provide an adhesive hydrogel fiber composite membrane that adapts to the mechanical properties of dynamic organs, as well as its preparation method and application. The hydrogel fiber composite membrane provided by the present invention can simultaneously meet the requirements of strong adhesion to wet tissue and biomechanical properties that adapt to dynamic organs.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides an adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs, comprising a micron fiber network scaffold layer, an electrospun nanofiber membrane layer deposited on both side surfaces and in the pore structure of the micron fiber network scaffold layer, wherein at least the electrospun nanofiber membrane layer on one side surface of the micron fiber network scaffold layer is loaded with porous self-gelling powder; the fibers of the micron fiber network scaffold layer and the electrospun nanofiber membrane layer are both polycaprolactone fibers.

[0006] Preferably, the fiber diameter of the micron fiber network scaffold layer is 1 to 10 μm, and the number of fiber layers is 1 to 50.

[0007] Preferably, the geometric structure of each fiber layer in the micron fiber network scaffold layer independently includes an auxetic structure or a non-auxetic structure, the auxetic structure includes a concave angle honeycomb network structure, a sinusoidal network structure or a diamond truss network structure, and the non-auxetic structure includes a quadrilateral network structure or a hexagonal network structure.

[0008] Preferably, the thickness of the electrospun nanofiber membrane layer is 50 to 200 μm; the fiber diameter of the electrospun nanofiber membrane layer is 500 nm to 1 μm.

[0009] Preferably, the average particle size of the porous self-gelling powder is 1 to 10 μm, and the porous self-gelling powder is a composite gel powder formed by polyacrylic acid and polyethyleneimine.

[0010] Preferably, the mass content of the porous self-gelling powder in the electrospun nanofiber membrane layer loaded with the porous self-gelling powder is 50 to 80%.

[0011] The present invention provides a method for preparing an adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs as described in the above technical solution, comprising the following steps:

[0012] Polycaprolactone was subjected to MEW printing to obtain a micron fiber network scaffold layer;

[0013] dissolving polycaprolactone in an organic solvent to obtain a spinning solution;

[0014] The spinning solution is electrospun and sprayed with porous self-gel powder on both sides of the micron fiber network scaffold layer to obtain the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties; the spraying of porous self-gel powder is carried out at least during the electrospinning process on one side of the micron fiber network scaffold layer.

[0015] Preferably, the MEW printing conditions include: heating polycaprolactone to form a polycaprolactone melt, the pumping pressure of the polycaprolactone melt is 0.2-1 bar, the distance from the print head to the receiving plate is 3-4 mm, the applied voltage is 3-5 kV, and the printing speed is 1000-1500 mm / min.

[0016] Preferably, the concentration of the spinning solution is 10-12% w / v, and the conditions for the electrospinning include: the flow rate of the spinning solution is 0.8-1 mL / h, the distance from the spinning needle to the receiving plate is 15-20 cm, the spinning voltage is 15-20 kV, the micron fiber network support layer is placed between the spinning needle and the receiving plate, and the distance between the micron fiber network support layer and the receiving plate is 5-10 cm.

[0017] The present invention provides the use of the adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs as described in the above technical solution or the adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs prepared by the preparation method described in the above technical solution in the preparation of tissue repair and / or regeneration materials, dynamic wound sealing materials, hemostatic and antibacterial materials and drug delivery materials.

[0018] The present invention provides an adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs, comprising a micron fiber network scaffold layer, an electrospun nanofiber membrane layer deposited on both sides of the micron fiber network scaffold layer and in a pore structure, wherein at least the electrospun nanofiber membrane layer on one side of the micron fiber network scaffold layer is loaded with porous self-gelling powder; the fibers of the micron fiber network scaffold layer and the electrospun nanofiber membrane layer are both polycaprolactone fibers. The hydrogel fiber composite membrane provided by the present invention has a "sandwich" structure, wherein the middle layer is a micron fiber network scaffold, which can be anisotropic by regulating the fiber diameter and scaffold geometric structure design parameters, thereby achieving personalized adaptation to the mechanical strength and nonlinear mechanical elasticity of dynamic organs; the surface of the micron fiber network scaffold layer is an electrospun nanofiber membrane loaded with porous self-gelling powder, which absorbs water at the tissue interface and rapidly gels in situ to form a hydrogel layer, and the functional groups in the polymer network at the hydrogel-tissue interface interact to achieve strong tissue adhesion. The hydrogel fiber composite membrane provided by the present invention can simultaneously meet the strong adhesion properties of wet tissue and adapt to the biomechanical properties of dynamic organs, and has broad application prospects in the fields of tissue repair and regeneration, dynamic wound sealing, hemostatic and antibacterial materials, and drug delivery. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the overall structure of the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties provided by the present invention. Figure 1 1-micrometer fiber network scaffold layer, 2-electrospun nanofiber membrane layer;

[0020] Figure 2 Schematic diagram of the geometric structure of the micron fiber network scaffold layer. Figure 2 (a) is a auxetic structure (recessed honeycomb network structure, sinusoidal network structure, diamond truss network structure), (b) is a non-auxetic structure (quadrilateral network structure, hexagonal network structure);

[0021] Figure 3 This is a scanning electron microscope image of the MEW micron fiber network scaffold with a sinusoidal structure in Example 1;

[0022] Figure 4 These are the stress-strain curves of the MEW micron fiber network scaffold with sinusoidal structure in Example 1 along the major axis and minor axis directions respectively. DETAILED DESCRIPTION

[0023] The present invention provides an adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs, comprising a micron fiber network scaffold layer, an electrospun nanofiber membrane layer deposited on both side surfaces and in the pore structure of the micron fiber network scaffold layer, wherein at least the electrospun nanofiber membrane layer on one side surface of the micron fiber network scaffold layer is loaded with porous self-gelling powder; the fibers of the micron fiber network scaffold layer and the electrospun nanofiber membrane layer are both polycaprolactone fibers.

[0024] Figure 1 This is a schematic diagram of the overall structure of the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties provided by the present invention. Figure 1 1-micron fiber network scaffold layer, 2-electrospun nanofiber membrane layer. The adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties provided by the present invention has a "sandwich" structure, which is described in detail below.

[0025] The adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties provided by the present invention includes a micron fiber network scaffold layer. In the present invention, the fibers of the micron fiber network scaffold layer are polycaprolactone (PCL) fibers. In the present invention, the fiber diameter of the micron fiber network scaffold layer is preferably 1 to 10 μm, specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 μm, and the number of fiber layers is preferably 1 to 50, specifically 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 layers; the thickness of the micron fiber network scaffold layer is the product of the fiber diameter and the number of fiber layers.

[0026] In the present invention, the geometric structure of each fiber layer in the micron fiber network scaffold layer preferably includes an auxetic structure or a non-auxetic structure. The auxetic structure preferably includes a concave angle honeycomb network structure, a sinusoidal network structure or a diamond truss network structure, and the non-auxetic structure preferably includes a quadrilateral network structure or a hexagonal network structure. In the present invention, the geometric structure of each fiber layer in the micron fiber network scaffold layer is as follows: Figure 2 As shown, Figure 2 (a) is a tensile structure (recessed honeycomb network structure, sinusoidal network structure, diamond truss network structure), (b) is a non-tensile structure (quadrilateral network structure, hexagonal network structure). Figure 2The enlarged views in the various sub-figures represent the structural units of the corresponding network structures, where w, h, and s represent the fiber spacing, and i represents the fiber angle. w and h are preferably 200-1000 μm, s is preferably 200-500 μm, and i is preferably 30°, 45°, or 60°, respectively. The amplitude in the sinusoidal structure is preferably 100-500 μm, and w and h represent the distances between adjacent intersections. By regulating w and h, the fiber network scaffold can be endowed with anisotropic characteristics, with an anisotropy ratio (i.e., anisotropic stiffness ratio, the ratio of the scaffold's Young's modulus in the transverse and longitudinal directions) preferably being 1-3. In the present invention, the auxetic structure has a negative Poisson's ratio and can adapt to the volumetric deformation of dynamic organs (such as the heart, stomach, and lungs). By regulating the fiber spacing, it can be endowed with anisotropic characteristics. The non-auxetic structure can adapt to tissues such as the diaphragm and tendons.

[0027] In natural tissues, the orderly arranged fiber network structure in the extracellular matrix (ECM) provides the mechanical strength and elasticity of the tissue. The hydrogel fiber composite membrane of the "sandwich" structure provided by the present invention uses a micron fiber network scaffold as the middle layer (i.e., a micron fiber network scaffold layer) with a fiber diameter (1 to 10 μm) that can replicate the diameter and structure of the fiber network in the ECM of natural tissues; the mechanical scalability of the fiber network scaffold can be improved by designing the scaffold geometric structure unit to be anisotropic and / or tensile structure; reducing the fiber spacing in the scaffold structure and increasing the number of fiber layers can improve the mechanical strength of the micron fiber network scaffold. Therefore, the micron fiber network scaffold layer can maintain mechanical strength and flexibility, thereby replicating the mechanical strength and nonlinear mechanical elasticity of natural tissues, enabling it to personalize and adapt to the biomechanical properties of dynamic organs, which is conducive to better integration of the composite fiber membrane with natural tissues.

[0028] The adhesive hydrogel fiber composite membrane provided by the present invention includes an electrospun nanofiber membrane layer deposited on both sides of the micron fiber network scaffold layer and in the pore structure, and at least the electrospun nanofiber membrane layer on one side of the micron fiber network scaffold layer is loaded with porous self-gelling powder (in some applications, only one side of the surface needs to be adhesive, so only the electrospun nanofiber membrane layer on one side of the micron fiber network scaffold layer needs to be loaded with porous self-gelling powder). In the present invention, the fiber of the electrospun nanofiber membrane layer is polycaprolactone fiber; the thickness of the electrospun nanofiber membrane layer is preferably 50 to 200 μm, specifically 50, 100, 150, or 200 μm; the fiber diameter of the electrospun nanofiber membrane layer is preferably 500 nm to 1 μm, specifically 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or 1 μm.

[0029] In the present invention, the porous self-gel powder is obtained by freeze-drying and pulverizing the hydrogel, and the average particle size of the porous self-gel powder is preferably 1 to 10 μm. In the present invention, the porous self-gel powder is preferably a composite gel powder formed by polyacrylic acid (PAA) and polyethyleneimine (PEI), and the mass ratio of PAA to PEI is preferably 1:1. In the present invention, the preparation method of the porous self-gel powder preferably includes the following steps:

[0030] A PEI aqueous solution (PEI molecular weight Mw, ca. 70,000) and a PAA aqueous solution (PAA molecular weight Mw, ca. 240,000) were mixed to obtain a PEI / PAA hydrogel;

[0031] The PEI / PAA hydrogel was immediately immersed in liquid nitrogen for about 15 minutes without pouring out any liquid, and freeze-dried to remove water to obtain a solid;

[0032] The solid is ground to obtain the porous self-gel powder.

[0033] In the present invention, the mass fraction of the PEI aqueous solution is preferably 10%, the mass fraction of the PAA aqueous solution is preferably 10%, and the volume ratio of the PEI aqueous solution to the PAA aqueous solution is preferably 1:1. In the present invention, the PEI and PAA polymers are cross-linked through strong non-covalent interactions (such as electrostatic interactions and hydrogen bonds) to form a dense, polyelectrolyte-rich gel-like complex, which is then freeze-dried and ground to obtain a self-gelling powder.

[0034] In the present invention, the mass content of the porous self-gelling powder in the electrospun nanofiber membrane layer loaded with the porous self-gelling powder is preferably 50 to 80%.

[0035] The present invention has a micron fiber network support layer on at least one side surface ( Figure 1 As shown, an electrospun nanofiber membrane loaded with a porous self-gelling powder (i.e., the electrospun nanofiber membrane layer) is employed in the upper and lower layers of the micronized fiber network scaffold layer. Due to the strong physical interaction between PEI and PAA polymers and the diffusion of free polymers, the PEI / PAA powder rapidly absorbs interfacial water on the tissue surface, rapidly forming a physically cross-linked hydrogel layer in situ without the need for additional cross-linking agents. Simultaneously, the physically cross-linked PEI / PAA polymers diffuse into the polymer network of wet tissue. The carboxylic acid and amine groups in the PEI / PAA hydrogel physically interact with functional groups (such as amines and thiols) on the wet tissue surface, further enhancing tissue adhesion.

[0036] Micro-nano fiber membranes have excellent mechanical properties, high porosity, and a biomimetic extracellular matrix structure, and can be used to enhance the mechanical properties of hydrogel adhesives. Combining self-gelling powder with electrospun nanofiber membranes can enhance the mechanical strength of hydrogel adhesives. However, the mechanical properties of a single-layer fiber membrane decrease with increasing self-gelling powder content. In addition, dense electrospun fiber membranes have poor mechanical elasticity and are unable to adapt to the nonlinear mechanical elasticity of natural soft tissues and the traction and expansion structure required for dynamic organ volume deformation. The present invention combines the strong wet tissue adhesion of self-gelling powder with the adjustable mechanical properties of micro-nano fiber scaffolds to provide a hydrogel fiber composite membrane with a "sandwich" structure. The electrospun nanofiber membrane layer on the surface contacts biological tissue and absorbs interfacial water, rapidly gelling in situ to form a hydrogel layer, achieving strong tissue adhesion. At the same time, the micron fiber scaffold in the middle layer is designed with an adjustable anisotropic-traction structure, which can adapt to the biomechanical characteristics of a wide range of dynamic organs (including anisotropic mechanical strength and nonlinear mechanical elasticity). This enables the composite membrane to simultaneously meet strong wet tissue adhesion and adapt to the biomechanical properties of dynamic organs.

[0037] The present invention provides a method for preparing an adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs as described in the above technical solution, comprising the following steps:

[0038] Polycaprolactone was subjected to MEW printing to obtain a micron fiber network scaffold layer;

[0039] dissolving polycaprolactone in an organic solvent to obtain a spinning solution;

[0040] The spinning solution is electrospun and sprayed with porous self-gel powder on both sides of the micron fiber network scaffold layer to obtain the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties; the spraying of porous self-gel powder is carried out at least during the electrospinning process on one side of the micron fiber network scaffold layer.

[0041] The present invention uses MEW printing (melt direct writing technology) to print polycaprolactone to obtain a micron fiber network scaffold layer. In the present invention, the weight-average molecular weight of the polycaprolactone (PCL) is preferably 450,000 to 650,000. In the present invention, the conditions for the MEW printing preferably include: heating the polycaprolactone to form a polycaprolactone melt, the pumping pressure of the polycaprolactone melt is 0.2 to 1 bar, the distance from the print head to the receiving plate is 3 to 4 mm, the applied voltage is 3 to 5 kV, and the printing speed (i.e., the receiving plate movement speed) is 1000 to 1500 mm / min. In the present invention, the heating temperature is preferably 80 to 90°C; the pumping pressure of the polycaprolactone melt is preferably controlled by an air pump, and the flow rate of the polycaprolactone melt is controlled by controlling the pumping pressure of the polycaprolactone melt; the diameter of the print head can be selected to be 0.3 mm or less, and the fiber diameter is mainly changed by adjusting the process parameters.

[0042] In the present invention, polycaprolactone is dissolved in an organic solvent to obtain a spinning solution. In the present invention, the weight-average molecular weight of the polycaprolactone is preferably 800,000 to 1,000,000, and the organic solvent is preferably acetone. The concentration of the spinning solution is preferably 10 to 12% w / v, specifically 10%, 11%, or 12% w / v (Note: 12% w / v means 12 g of solute per 100 ml of solution).

[0043] After obtaining the micron fiber network scaffold layer and the spinning solution, the present invention uses the spinning solution to electrospin the two side surfaces of the micron fiber network scaffold layer and spray porous self-gel powder to obtain the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties; the spraying of porous self-gel powder is carried out at least during the electrospinning process of one side surface of the micron fiber network scaffold layer.

[0044] In the present invention, the specific operation of electrospinning the spinning solution on both sides of the micron fiber network scaffold layer is as follows: electrospinning one side of the micron fiber network scaffold layer, then turning the micron fiber network scaffold layer over and using the other side as the receiving surface for electrospinning fibers. In the present invention, the conditions for electrospinning preferably include: a flow rate of the spinning solution of 0.8 to 1 mL / h, a distance from the spinning needle to the receiving plate of 15 to 20 cm, a spinning voltage of 15 to 20 kV, the micron fiber network scaffold layer being placed between the spinning needle and the receiving plate, and the distance between the micron fiber network scaffold layer and the receiving plate being 5 to 10 cm. In the present invention, the spinning needle is preferably a needle with a specification of 21G, and the thickness of the electrospun nanofiber membrane layer is controlled by the spinning time. In the present invention, the porous self-gelling powder is preferably sprayed by a blower. The sprayed self-gelling powder and the nanofibers (dense electrospun nanofibers as a carrier) are firmly, uniformly and stably combined in the electrospinning path (in the air) through electrostatic adsorption, and are ultimately deposited and entangled on the micron fiber network scaffold to form a "sandwich" structure of the hydrogel fiber composite membrane. In the present invention, the loading amount of the porous self-gelling powder in the nanofibers is controlled by adjusting the spray airflow velocity of the porous self-gelling powder (10 to 30 kPa); the electrospun nanofibers can penetrate the micron fiber network scaffold layer and entangle and cover its surface.

[0045] The present invention provides the use of the adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs as described in the above technical solution or the adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs obtained by the preparation method described in the above technical solution in the preparation of tissue repair and / or regeneration materials, dynamic wound sealing materials, hemostatic and antibacterial materials and drug delivery materials. The hydrogel fiber composite membrane provided by the present invention can simultaneously meet the strong adhesion to wet tissue and the biomechanical properties adapted to dynamic organs, and has broad application prospects in the fields of tissue repair and regeneration, dynamic wound sealing, hemostatic and antibacterial materials and drug delivery. The present invention has no special requirements for the method of application, and the application method familiar to those skilled in the art can be used.

[0046] To further illustrate the present invention, the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties, its preparation method and application provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of protection of the present invention.

[0047] Example 1

[0048] Preparation of an adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties is as follows:

[0049] (1) Preparation of porous self-gel powder (polyacrylic acid (PAA) and polyethyleneimine (PEI) composite gel, denoted as PAA / PEI porous self-gel powder)

[0050] Equal volumes of PEI aqueous solution (molecular weight, Mw, ca. 70,000; mass fraction, 10%) and PAA aqueous solution (Mw, ca. 240,000; mass fraction, 10 wt%) were mixed. The resulting PEI / PAA composite gel was immediately immersed in liquid nitrogen for approximately 15 minutes without decanting any liquid and freeze-dried to remove moisture. Finally, the dried solid was ground to obtain PAA / PEI self-gel powder with a particle size of 1 to 10 μm.

[0051] (2) Hydrogel fiber composite membrane ( Figure 1 As shown) and its preparation

[0052] This embodiment provides a "sandwich" structure hydrogel fiber composite membrane, which consists of a fiber network scaffold 1 in the middle layer and an electrospun nanofiber membrane 2 loaded with porous self-gel powder in the upper and lower layers. The fiber network scaffold 1 has a geometric structure of a tensile expansion structure - a sinusoidal network structure (such as Figure 2 shown).

[0053] The preparation of the hydrogel fiber composite membrane is as follows:

[0054] A micron fiber network scaffold 1 was printed using melt direct writing (MEW) technology. The printing process parameters were as follows: molten polycaprolactone (PCL, molecular weight Mw 450,000) was heated at a constant temperature of 90°C. The flow rate of the molten PCL was controlled by an air pump with a set pump pressure of 0.2 bar. The distance between the print head and the receiving plate was 4 mm. The applied voltage was 3.5 kV. The printing speed (receiving plate movement speed) was 1000 mm / min. A sinusoidal MEW micron fiber network scaffold (fiber diameter 10 μm, fiber spacing w (minor axis direction) 400 μm, fiber spacing h (major axis direction) 800 μm, amplitude 100 μm, and number of fiber layers 5) was obtained.

[0055] Polycaprolactone powder (molecular weight Mw 800000) was dissolved in acetone solution to prepare a 10% w / v spinning solution;

[0056] The fiber network support 1 is placed between the electrospinning needle and the receiving plate, and the distance between the micron fiber network support layer and the receiving plate is 5 cm. The nanofiber membrane 2 loaded with porous self-gelling powder is collected. The electrospinning process conditions are as follows: the spinning solution flow rate is 1 mL / h, the distance from the spinning needle to the receiving plate is 20 cm, the spinning voltage is 20 kV, the PAA / PEI porous self-gelling powder (prepared in step (1) of Example 1) is ejected by a blower, and is firmly and evenly combined with the PCL nanofibers in the air through electrostatic adsorption in the electrospinning path. The loading amount of the porous self-gelling powder is controlled by adjusting the powder injection air flow velocity (10-30 kPa), and then deposited and wound together on the micron fiber support 1, finally forming a "sandwich" structure hydrogel composite fiber membrane. The thickness of the electrospun nanofiber membrane 2 is 50-200 μm, the fiber diameter is 500 nm-1 μm, and the mass content of the porous self-gelling powder in the electrospinning nanofiber membrane layer is 50-80%.

[0057] Figure 3 This is a scanning electron microscope image of the MEW micron fiber network scaffold with a sinusoidal structure in Example 1.

[0058] The stress-strain curves of the MEW micron fiber network scaffold in Example 1 along the long axis and short axis were tested by uniaxial tensile test using a tensile tester (Instron 5944). Figure 4 As shown, the microfiber network scaffold exhibits a J-shaped stress-strain response similar to that of natural soft tissue. Line fitting of the elastic region of the sample's stress-strain curve revealed a Young's modulus (E1) of 1.00 MPa along the major axis and 0.47 MPa (E2) along the minor axis, resulting in an anisotropic modulus ratio (E1 / E2) of 2.13.

[0059] Example 2

[0060] The MEW micron fiber network scaffold with the sinusoidal structure in Example 1 was replaced with a micron fiber network scaffold with the following structure, and the rest was the same as in Example 1:

[0061] The fiber network support 1 has a support geometry of a tensile structure (a concave angle honeycomb network structure or a diamond truss network structure) or a non-tensile structure (a quadrilateral network structure or a hexagonal network structure) (e.g. Figure 2 As shown in FIG, the fiber diameter is 1 to 10 μm, the number of fiber printing layers is 1 to 50, the fiber spacing w and h are 200 to 1000 μm, the fiber spacing s is 200 to 500 μm, and the fiber angle i is 30°, 45°, or 60°.

[0062] The sandwich-structured hydrogel-fiber composite membrane provided by the present invention rapidly gels in situ upon contact with biological tissue and absorption of interfacial water, forming a hydrogel layer. This achieves strong tissue adhesion, while the micronized fiber scaffold in the middle layer maintains mechanical strength and nonlinear elasticity. The hydrogel-fiber composite membrane provided by the present invention achieves both strong adhesion to wet tissue and biomechanical properties that adapt to dynamic organs.

[0063] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation thereto. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications shall also be considered within the scope of protection of the present invention.

Claims

1. An adhesive hydrogel fiber composite membrane adapted to the mechanical properties of dynamic organs, comprising a micronized fiber network scaffold layer, and an electrospun nanofiber membrane layer deposited on both sides of the micronized fiber network scaffold layer and within its pore structure, wherein at least one surface of the micronized fiber network scaffold layer is loaded with a porous self-gelling powder; the fibers of both the micronized fiber network scaffold layer and the electrospun nanofiber membrane layer are polycaprolactone fibers; The geometric structure of each fiber layer in the micron fiber network scaffold layer is an auxetic structure, and the auxetic structure includes a concave angle honeycomb network structure, a sinusoidal network structure or a diamond truss network structure; The average particle size of the porous self-gel powder is 1-10 μm, and the porous self-gel powder is a composite gel powder formed by polyacrylic acid and polyethyleneimine; The mass content of the porous self-gelling powder in the electrospun nanofiber membrane layer loaded with the porous self-gelling powder is 50-80%.

2. The adhesive hydrogel fiber composite membrane adapted to dynamic organ mechanical properties according to claim 1, characterized in that: The fiber diameter of the micron fiber network scaffold layer is 1-10 μm, and the number of fiber layers is 1-50.

3. The adhesive hydrogel fiber composite membrane adapted to dynamic organ mechanical properties according to claim 1, characterized in that: The thickness of the electrospun nanofiber membrane layer is 50-200 μm; the fiber diameter of the electrospun nanofiber membrane layer is 500 nm-1 μm.

4. The method for preparing the adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs according to any one of claims 1 to 3, characterized in that: The following steps are involved: Polycaprolactone was subjected to MEW printing to obtain a micron fiber network scaffold layer; dissolving polycaprolactone in an organic solvent to obtain a spinning solution; The spinning solution is electrospun and sprayed with porous self-gel powder on both sides of the micron fiber network scaffold layer to obtain the adhesive hydrogel fiber composite membrane adapted to the dynamic organ mechanical properties; the spraying of porous self-gel powder is carried out at least during the electrospinning process on one side of the micron fiber network scaffold layer.

5. The preparation method according to claim 4, characterized in that The MEW printing conditions include: heating polycaprolactone to form a polycaprolactone melt, the pumping pressure of the polycaprolactone melt is 0.2-1 bar, the distance from the print head to the receiving plate is 3-4 mm, the applied voltage is 3-5 kV, and the printing speed is 1000-1500 mm / min.

6. The preparation method according to claim 4, characterized in that The concentration of the spinning solution is 10-12% w / v. The electrospinning conditions include: a spinning solution flow rate of 0.8-1 mL / h, a distance from the spinning needle to the receiving plate of 15-20 cm, a spinning voltage of 15-20 kV, and a micron fiber network scaffold layer placed between the spinning needle and the receiving plate, with the distance between the micron fiber network scaffold layer and the receiving plate being 5-10 cm.

7. Use of the adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs as described in any one of claims 1 to 3 or the adhesive hydrogel fiber composite membrane adapted to the dynamic mechanical properties of organs prepared by the preparation method according to any one of claims 4 to 6 in the preparation of tissue repair and / or regeneration materials, dynamic wound sealing materials, hemostatic and antibacterial materials, and drug delivery materials.

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