CN114618021B - Intelligent bionic tendon scaffold and preparation method thereof - Google Patents
Intelligent bionic tendon scaffold and preparation method thereof Download PDFInfo
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Abstract
The invention provides an intelligent bionic tendon scaffold and a preparation method thereof, wherein the intelligent bionic tendon scaffold is made of a mixed material comprising a degradable material, a piezoelectric material and a performance enhancing material; the bracket is provided with a multi-layer fiber structure, and fiber filaments of two adjacent layers of fiber structures are arranged in a crossing manner; and forming microstructure units in the vertical section of the multi-layer fiber structure, wherein at least one part of the microstructure units are negative poisson ratio structure units. The invention provides a degradable highly bionic tendon scaffold, which is designed by taking a degradable polymer as a matrix material, introducing a piezoelectric material, a mechanical property and a conductivity reinforcing material, and endowing the degradable tendon scaffold with sufficient mechanical property and piezoelectric property. When the microstructure of the tendon scaffold is designed, fiber structure distribution and multi-dimension size distribution of the fiber structure are innovatively designed, and the tendon scaffold is endowed with conditions that the tendon scaffold can be matched with the morphological characteristics of natural tissues and the mechanical deformation effect.
Description
Technical Field
The invention relates to the field of human tissue injury repair, in particular to an intelligent bionic tendon scaffold and a preparation method thereof.
Background
Tendons are connective tissues connecting muscles and bones, and the existence of the tendons realizes the transmission of muscle contraction force to bones, and ensures normal life activities of human bodies. However, tendinosis is one of the common and frequently occurring diseases of orthopedics, accounting for 30% of musculoskeletal diseases. For the elderly and athletes, the incidence of tendinopathy is higher than that of the general population due to age degeneration or overuse of tendons. It is counted that more than 1 hundred million tendon injury cases are caused each year worldwide, and the economic burden of about 127 hundred million RMB is brought about while the body limb dysfunction and even disability are caused. At present, the incidence rate of the disease is in an increasing trend year by year along with the general increase of physical activities such as population aging and running, walking and the like in China. However, due to insufficient blood supply of tendons, regeneration capacity of the tendons is very limited, so that the tendons are also faced with great challenges in clinic, and innovative treatment methods are urgently needed to meet the health requirements of national citizens in China.
Traditional therapeutic strategies for tendon injury have focused on pain relief, inflammation relief, and restoration of partial function. The gold standard of clinical treatment is tendon repair using sutures, autografts, allografts and xenografts, which, although relatively successful, often fail to restore the full function of the tendon, with re-rupture being a major potential complication. With the development of biomedical engineering, tissue engineering scaffolds provide a potential therapeutic approach for restoring tendon tissue structure and function.
The tendon is mainly composed of parallel collagen fiber bundles, has no contractility, and has connective tissue membrane coated on the surface, and a small amount of connective tissue is connected between the collagen fibers. The tendon is used as compact connective tissue, has piezoelectric property, can generate electric signals under the action of external force, and can regulate the growth of tenocyte and the repair of tissue. The tendon has strong toughness, strong anti-expansion capability and typical nonlinear mechanical property under the action of mechanical load.
In addition, tendons have another unique mechanical response, namely a negative poisson's ratio effect, which brings different mechanical stimulation conduction modes to tissue cells, and early studies show that a negative poisson's ratio bracket can promote tissue growth. Therefore, the tendon scaffold with geometrical structural characteristics, mechanical response characteristics and piezoelectric characteristics similar to tendon tissues is considered to be designed, can provide a surface morphology, piezoelectric and dynamic and static mechanical microenvironment similar to that of natural tissues for tenocytes in repairing damaged tendons, and has the functions of promoting directional cell arrangement, growth, proliferation and differentiation, tendinous differentiation and regeneration of tendon tissues. However, the prior art lacks a bionic scaffold aiming at the characteristics of tendons, and under the background, the bionic tendon scaffold which can simulate the tendon collagen fiber bundle structure can be found, so that the bionic tendon scaffold has very important significance in the field.
Disclosure of Invention
The technical problem that prior art lacks the bionic tendon support that can simulate tendon collagen fiber bundle structure that this application was solved, and then provide a degradable can also provide with tendon tissue similar piezoelectricity microenvironment and quiet, dynamic mechanics microenvironment simultaneously, promote the intelligent bionic tendon support of tendon tissue regeneration, this application still provides simultaneously the preparation method of intelligent bionic tendon support.
The technical method adopted for solving the technical problems is as follows:
an intelligent bionic tendon scaffold is prepared from a mixed material comprising a degradable material, a piezoelectric material and a performance enhancing material; the bracket is provided with a multi-layer fiber structure, and fiber filaments of two adjacent layers of fiber structures are arranged in a crossing manner; and forming microstructure units in the vertical section of the multi-layer fiber structure, wherein at least one part of the microstructure units are negative poisson ratio structure units.
The degradable material is polycaprolactone; the piezoelectric material is barium titanate powder; the performance enhancing material adopts graphene sheets.
The molecular weight of the polycaprolactone ranges from 5000 to 10000, the particle size of the barium titanate powder ranges from 50 to 200nm, and the thickness of the graphene sheet ranges from 5 to 100nm.
The bracket is formed by intersecting and distributing a transverse fiber layer and a longitudinal fiber layer, and longitudinal fiber filaments in two adjacent longitudinal fiber layers are staggered; two adjacent longitudinal fiber filaments in the same layer prop open the transverse fiber filaments positioned above and below to form a basic structural unit; longitudinal fiber filaments above and below the basic structural unit squeeze the basic structural unit to form the concave negative poisson ratio structural unit.
The transverse fiber filaments and the longitudinal fiber filaments of the bracket are perpendicular to each other, and the diameter of the longitudinal fiber filaments is larger than that of the transverse fiber filaments.
The pore diameter of the microporous structure of the bracket ranges from 10 to 1000 mu m, and the porosity range is preferably 5 to 84 percent.
The elastic modulus of the bracket ranges from 54 MPa to 660MPa, the ultimate strength ranges from 20 MPa to 70MPa, the negative Poisson ratio ranges from-7 to-1, and the piezoelectric coefficient ranges from 0.2 pC/N to 2.0pC/N.
The preparation method of the intelligent bionic tendon scaffold comprises the following steps:
(1) Preparing a mixed material of a degradable material, a piezoelectric material and a performance enhancing material by adopting a solvent blending method or a high-temperature heating and melting mixing method;
(2) According to the microstructure unit design of the scaffold, the tendon scaffold is prepared by a three-dimensional deposition 3D printing method.
In the step (1), the mechanical property, the piezoelectric property, the degradation property and the biological property of the mixed material are evaluated firstly, and the proportion of the mixed material suitable for the tendon scaffold is determined.
In the step (2), the tendon scaffold is prepared by any one 3D printing method of three-dimensional fiber deposition, photo-curing, laser sintering and electron beam sintering.
In the step (2), the method for preparing the tendon scaffold by a three-dimensional fiber deposition 3D printing method comprises the following steps: a. the fiber diameter, the distribution interval and the layer number are designed through programming, an initial three-dimensional model of the fiber-like distributed tendon scaffold is built through three-dimensional modeling software, when the model is built, two adjacent layers of fibers are designed to be staggered and overlapped and distributed and have different diameters, and a basic model is provided for the subsequent realization of scaffold manufacturing with crimped fibers and negative poisson ratio effects through adjusting printing parameters; b. the method comprises the steps of guiding an initial support three-dimensional model into 3D printing slicing software for slicing treatment, adopting a high-temperature melting or normal-temperature solvent melting printing mode, utilizing the characteristics of gravity effect and fine fiber yarn bearing bending deformation when fiber yarn is not solidified, realizing the bending deformation of the fiber yarn by adjusting printing parameters including temperature, pressure, speed, waiting time and the like, regulating and controlling the geometric shape of a micropore structure constructed by the fiber yarn, and preparing a fiber-like distributed negative poisson ratio tendon support by printing layer by layer to optimize 3D printing parameters so as to realize the manufacturing of the fiber-like distributed negative poisson ratio tendon support.
The method for preparing the tendon scaffold by the 3D printing method of photo-curing, laser sintering and electron beam sintering comprises the following steps: a. designing a porous bracket with a negative poisson effect by adopting three-dimensional modeling software; b. and (3) importing the three-dimensional model of the porous scaffold with the negative poisson effect into 3D printing slicing software to perform slicing treatment, and adjusting printing parameters including temperature, speed, scanning path and the like to realize the manufacturing of the fiber-like distributed negative poisson ratio tendon scaffold.
The intelligent bionic tendon scaffold and the preparation method thereof have the advantages that:
the intelligent bionic tendon scaffold provided by the invention is degradable and highly bionic by means of scaffold materials, scaffold microstructure design and scaffold 3D printing parameter regulation and control. In the material design of the tendon support, a degradable polymer is used as a matrix material, and a piezoelectric material, a mechanical property and a conductivity reinforcing material are introduced, so that the degradable tendon support is endowed with sufficient mechanical property and piezoelectric property. When the microstructure of the tendon scaffold is designed, fiber structure distribution and multi-dimension size distribution of the fiber structure are innovatively designed, and the tendon scaffold is endowed with conditions that the tendon scaffold can be matched with the morphological characteristics of natural tissues and the mechanical deformation effect.
The pore diameter range of the microporous structure of the scaffold is preferably 10-1000 mu m, and the porosity range is preferably 5-84%, so that the scaffold has the morphological characteristics capable of matching natural tissues. Meanwhile, the elastic modulus of the bracket ranges from 54 MPa to 660MPa, the ultimate strength ranges from 20 MPa to 70MPa, the negative poisson ratio ranges from-7 to-1, and the piezoelectric coefficient ranges from 0.2 pC/N to 2.0pC/N. The degradability, the piezoelectric effect and the negative poisson ratio effect of the tendon scaffold can realize that the invented scaffold can treat tendon injury in vivo: in the treatment period, under the physiological environment, bioelectricity and mechanical microenvironment of bionic tendon tissues can be provided for tenocytes and tissues, and damaged tissue regeneration is promoted; after the treatment is finished, tendon injury repair is completed, the stent is automatically degraded and absorbed by a human body, and the stent can not be used as a foreign body to stay in the body for a long time, so that the infection risk can be effectively avoided. The tendon scaffold has wide application prospect in the field of repairing tendon tissue morphology and functions.
According to the preparation method of the tendon stent, a three-dimensional deposition 3D printing technology is adopted, and aiming at the property of printing materials, the manufacturing of the stent is accurately realized by adjusting printing parameters such as printing speed, residence time, printing pressure and the like.
In order to make the technical scheme of the intelligent bionic tendon scaffold and the preparation method thereof more clear, the invention is further described below with reference to the accompanying drawings and the specific embodiments.
Drawings
FIG. 1 is a diagram showing the structure of an intelligent bionic tendon scaffold according to the present invention;
fig. 2 is a schematic diagram of a negative poisson ratio structural unit of the intelligent bionic tendon scaffold according to the present invention, which is an enlarged view of a portion a in fig. 1.
FIG. 3 is a front view of a three-dimensional model of an initially designed porous scaffold;
FIG. 4 is a top view of a three-dimensional model of the original design porous scaffold;
FIG. 5 is a left side view of the three-dimensional model of the porous scaffold as originally designed;
wherein the reference numerals are as follows:
1-longitudinal fiber filaments; 2-transverse filaments.
Detailed Description
The embodiment provides an intelligent bionic tendon scaffold which is made of a mixed material comprising a degradable material, a piezoelectric material and a performance enhancing material; in the embodiment, the degradable polymer Polycaprolactone (PCL) is taken as a degradable material, and the barium titanate (BaTiO) with piezoelectric effect is introduced 3 ) The material, the mechanical property and the conductivity enhanced Graphene (Graphene) material are performance enhanced materials. The molecular weight of the polycaprolactone ranges from 5000 to 10000, the particle size of the barium titanate powder ranges from 50 to 200nm, and the thickness of the graphene sheet ranges from 5 to 100nm.
In this embodiment, the intelligent bionic tendon scaffold has a multi-layer fiber structure, as shown in fig. 1, fiber filaments of two adjacent layers of fiber structures are arranged in a crossing manner; microstructure units are formed in a vertical section of the multi-layer fiber structure, at least a part of the microstructure units are negative poisson ratio structure units, and in the embodiment, the vertical section is a section perpendicular to the longitudinal fiber filaments 1. The bracket is formed by intersecting and distributing a transverse fiber layer and a longitudinal fiber layer, and longitudinal fiber filaments 1 in two adjacent longitudinal fiber layers are staggered; two adjacent longitudinal fiber filaments 1 in the same layer prop open the transverse fiber filaments 2 positioned above and below to form a structural unit, as shown in figure 2; in this embodiment, the transverse filaments 2 and the longitudinal filaments 1 of the stent are perpendicular to each other, and the diameter of the longitudinal filaments 1 is larger than the diameter of the transverse filaments 2. Longitudinal fiber filaments 1 positioned above and below the structural units squeeze the structural units to form concave negative poisson ratio structural units. In fig. 2, the negative poisson's ratio structural unit is spread by two longitudinal fiber filaments 1 to form a structure with a basically concave hexagonal shape, and the angle of θ of the concave hexagonal structure is smaller than 90 °. The span of the concave hexagon in the transverse direction is L 1 The highest height of the two sides of the concave hexagon is L 2 As a preferable arrangement, the span L 1 Greater than height L 2 . The diameter of the transverse fiber filaments 2 is smaller than that of the longitudinal fiber filaments 1, and the transverse fiber filaments 2 in one transverse fiber filament layer are arranged in the longitudinal directionThere are several groups, each group comprising a number of immediately arranged transverse filaments 2, in this embodiment 4 immediately arranged transverse filaments 2.
When the microstructure of the tendon scaffold is designed, the fiber structure distribution and the multi-dimension scale distribution are designed, so that the tendon scaffold can be matched with the morphological characteristics and the mechanical deformation effects of natural tissues; the pore diameter of the microporous structure of the bracket formed by the multi-layer fiber structure ranges from 10 mu m to 1000 mu m, and the porosity range is preferably 5 to 84 percent. The communication rate can reach 100 percent, and the natural tendon tissue morphology feature can be matched.
The design and manufacturing steps of the intelligent bionic tendon scaffold in the embodiment are as follows: (1) The solvent blending method or the high-temperature heating and melting mixing method is adopted to prepare the polycaprolactone-barium titanate-graphene (PCL-BaTiO) with different proportions 3 -G) a mixed material; (2) Evaluation of PCL-BaTiO 3 -mechanical property, piezoelectric property, degradation property and biological property of the G mixed material, and determining the ratio of the mixed material suitable for the tendon scaffold; (3) According to the embodiment, the tendon scaffold is prepared by a three-dimensional fiber deposition 3D printing method, the diameter, the distribution interval and the layer number of fibers are designed by programming, an initial three-dimensional model of the fiber-like distributed tendon scaffold is built by three-dimensional modeling software, as shown in figures 3-5, when the model is built, two adjacent layers of fibers are designed to be in staggered lap joint distribution and have different diameters, and a basic model is provided for the subsequent realization of scaffold manufacturing with crimped fibers and negative poisson ratio effect by adjusting printing parameters; (4) The method comprises the steps of guiding an initial support three-dimensional model into 3D printing slicing software for slicing treatment, adopting a high-temperature melting or normal-temperature solvent melting printing mode, utilizing the characteristics of gravity effect and fine fiber yarn bearing bending deformation when fiber yarn is not solidified, realizing the bending deformation of the fiber yarn by adjusting printing parameters including temperature, pressure, speed, waiting time and the like, regulating and controlling the geometric shape of a micropore structure constructed by the fiber yarn, and preparing a fiber-like distributed negative poisson ratio tendon support by printing layer by layer to optimize 3D printing parameters so as to realize the manufacturing of the fiber-like distributed negative poisson ratio tendon support.
The elastic modulus of the tendon scaffold prepared by the embodiment ranges from 54 MPa to 660MPa, the ultimate strength ranges from 20 MPa to 70MPa, the negative poisson ratio ranges from-7 to-1, the piezoelectric coefficient ranges from 0.2 pC/N to 2.0pC/N, and the tendon scaffold has mechanical deformation effect conditions matched with tendons.
As an alternative embodiment, the degradable polymer matrix material may be other degradable polymer materials with better biocompatibility; the piezoelectric effect material can be piezoelectric ceramics and piezoelectric polymers with better biocompatibility except barium titanate; besides graphene, the material with enhanced mechanical properties and conductivity can also be other materials with enhanced mechanical properties and conductivity with better biocompatibility, such as graphite alkyne, graphene oxide, graphite alkyne oxide and the like.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the protection scope of the present invention is subject to the claims.
Claims (6)
1. The intelligent bionic tendon scaffold is characterized by being made of a mixed material of a degradable material, a piezoelectric material and a performance enhancing material, wherein the degradable material is polycaprolactone, the piezoelectric material is barium titanate, and the performance enhancing material is graphene;
the bracket is provided with a multi-layer fiber structure, and fiber filaments of two adjacent layers of fiber structures are arranged in a crossing manner; forming microstructure units in a vertical section of the multi-layer fiber structure, wherein at least a part of the microstructure units are negative poisson ratio structure units;
the bracket is formed by intersecting and distributing a transverse fiber layer and a longitudinal fiber layer, longitudinal fiber filaments in two adjacent longitudinal fiber layers are staggered, and a plurality of groups of transverse fiber filaments in one transverse fiber filament layer are arranged in the longitudinal direction; two adjacent longitudinal fiber filaments in the same layer prop open the transverse fiber filaments positioned above and below to form a structural unit; longitudinal fiber filaments positioned above and below the structural unit squeeze the structural unit to form a concave negative poisson ratio structural unit;
the transverse fiber filaments and the longitudinal fiber filaments of the bracket are mutually perpendicular, and the diameter of the longitudinal fiber filaments is larger than that of the transverse fiber filaments;
the pore diameter range of the microporous structure of the bracket is 10-1000 mu m, and the porosity range is 5-84%; the elastic modulus of the support ranges from 54 MPa to 660MPa, the ultimate strength ranges from 20 MPa to 70MPa, the negative Poisson ratio ranges from-7 to-1, and the piezoelectric coefficient ranges from 0.2 pC/N to 2.0pC/N.
2. The intelligent bionic tendon scaffold according to claim 1, wherein the piezoelectric material is barium titanate powder; the performance enhancing material adopts graphene sheets.
3. The intelligent bionic tendon scaffold according to claim 2, wherein the molecular weight of polycaprolactone ranges from 5000 to 10000, the particle size of barium titanate powder ranges from 50 to 200nm, and the thickness of graphene sheets ranges from 5 to 100nm.
4. A method for preparing an intelligent bionic tendon scaffold according to any one of claims 1 to 3, comprising the steps of:
(1) Preparing a mixed material of a degradable material, a piezoelectric material and a performance enhancing material by adopting a solvent blending method or a high-temperature heating and melting mixing method;
(2) According to the microstructure unit design of the scaffold, the tendon scaffold is prepared by a three-dimensional deposition 3D printing method.
5. The method for preparing an intelligent bionic tendon scaffold according to claim 4, wherein in the step (1), the mechanical property, piezoelectric property, degradation property and biological property of the mixed material are evaluated first, and the proportion of the mixed material suitable for the tendon scaffold is determined.
6. The method for preparing an intelligent bionic tendon scaffold according to claim 5, wherein in the step (2), the tendon scaffold is prepared by any one of 3D printing methods of three-dimensional fiber deposition, photo-curing, laser sintering and electron beam sintering.
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