CN115970050A - Double-layer film for tissue engineering small blood vessel or blood vessel stent and preparation and application thereof - Google Patents
Double-layer film for tissue engineering small blood vessel or blood vessel stent and preparation and application thereof Download PDFInfo
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- CN115970050A CN115970050A CN202211513752.9A CN202211513752A CN115970050A CN 115970050 A CN115970050 A CN 115970050A CN 202211513752 A CN202211513752 A CN 202211513752A CN 115970050 A CN115970050 A CN 115970050A
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 78
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
The invention discloses a double-layer film for a tissue engineering small blood vessel or a blood vessel stent, wherein one layer is a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2-0.4 mm, which is prepared by printing ink prepared from regenerated chitosan/polyvinyl alcohol through 3D printing, and the other layer is a non-water-soluble degradable polymer film with the thickness of 0.4-0.6 mm, which is prepared by printing ink prepared from a non-water-soluble degradable polymer with good biocompatibility through 3D printing on the surface of the regenerated chitosan/polyvinyl alcohol film. Each layer has good blood compatibility and biocompatibility. The double-layer film is self-curled into a tubular object with the inner diameter of 4.0-6.0 mm and the wall thickness of 0.4-0.8 mm under the stimulation of a liquid environment, and further can be self-expanded to the inner diameter of 8.0-10.0 mm under the stimulation of the liquid environment. The invention can be applied to preparing small vessels of tissue engineering or vascular stents with self-expansion function.
Description
Technical Field
The invention relates to a tissue engineering small blood vessel and a blood vessel stent, in particular to a double-layer film for the tissue engineering small blood vessel or the blood vessel stent and a preparation method thereof.
Background
Cardiovascular diseases are main diseases threatening human health, and the latest research report of the world health organization shows that the number of people dying from cardiovascular and cerebrovascular diseases in 2019 all over the world is about 1790 thousands of people, and the people live at the first position of various causes of death. The tissue engineering blood vessel or the blood vessel stent is used for interventional medical treatment, and becomes a main means for treating cardiovascular diseases due to the advantages of small wound, quick response, high success rate of operation and the like.
The tissue engineering blood vessel is a blood vessel tissue substitute which is manufactured by imitating the composition and physiological function of an ideal blood vessel and has certain biocompatibility. The clinical application effect of the current large-caliber artificial blood vessel is ideal, but the effect of the small-caliber artificial blood vessel (the diameter is less than or equal to 6 mm) is not satisfactory, thrombus is easy to form, and rapid endothelialization is considered as the key for solving the problem. In this case, tissue engineering small blood vessels are produced, and before implantation, endothelial cells are spread on the inner surface of the artificial small blood vessels to promote proliferation and differentiation and endothelialization, which can not only reduce the platelet adhesion rate and hemolysis rate of the material, but also reduce the activity of prothrombin on the inner surface of the blood vessels. However, the implantation of endothelial cells in artificial small blood vessels is difficult to operate and difficult to form a uniform cell layer; also, the size of the small blood vessels varies from patient to patient and from lesion to lesion, and therefore, a simple method of constructing tissue-engineered small blood vessels is required to meet clinical needs in emergency.
Different from small vessels in tissue engineering, the vascular stent is mainly placed in a diseased vessel section to achieve the purposes of supporting the vessel at a stenotic occlusion section, reducing the elastic retraction and reshaping of the vessel and keeping the blood flow of a lumen unobstructed. At present, metal stents are used more, but the metal stents have the defects of poor blood compatibility, late stent restenosis and the like. In contrast, the shape memory polymer vascular stent not only has good blood compatibility and processability, but also can spontaneously generate controllable shape recovery under external stimulation to prop open a narrow blood vessel at a lesion, and is one of the forefront directions in the research field of the current novel vascular stent. The Chinese patent with the application number of CN202110353590.6 discloses an anti-restenosis 3D printing self-expanding degradable intravascular stent and a preparation method thereof, and the stent can realize water response self-expansion to open a stenotic blood vessel through a degradable high polymer intravascular stent prepared by 3D printing. Similar to small vessels in tissue engineering, the size of the stent required varies from patient to patient and from lesion site to lesion site, and a simple method of constructing the stent is also required to meet clinical needs in emergency.
In tissue engineering of small vessels, researchers developed a technique for converting 2D scaffolds into 3D structures because 2D structures are easy to fabricate and cells are easy to implant. For example, cheng et al combines cell patterning technology on a plane with stress-induced self-curling technology to achieve layered distribution of various cells on a three-dimensional tubular structure, so that small tissue-engineered vessels can be rapidly obtained (Cheng S, et al adv Mater 2017 1700171. However, in terms of the vascular stent, there is no technology that can rapidly construct a vascular stent of a desired size as needed. Moreover, at present, no technology or material exists, and in an emergency situation, a tissue engineering small vessel or a vessel stent can be obtained rapidly and simultaneously according to needs.
Disclosure of Invention
Aiming at the prior art, the invention provides a double-layer film for a tissue engineering small blood vessel or a blood vessel stent, which is formed by compounding two layers of water-insoluble polymers with different thicknesses and chitosan/polyvinyl alcohol, wherein the chitosan/polyvinyl alcohol can generate self-curling behavior through liquid environment stimulation, so that the blood vessel stent can plant endothelial cells on the surface of regenerated chitosan/polyvinyl alcohol and obtain the tissue engineering small blood vessel with required size through self-curling through liquid environment stimulation; or the vessel stent with the required size can be manufactured according to the requirement, and then the self-expansion is realized through the stimulation of a liquid environment.
In order to solve the technical problem, the invention provides a double-layer film for a tissue engineering small blood vessel or a blood vessel stent, which is prepared by 3D printing, wherein one layer is a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2-0.4 mm prepared by printing ink prepared from chitosan/polyvinyl alcohol through 3D printing, and the other layer is a non-water-soluble degradable polymer film with the thickness of 0.4-0.6 mm prepared by printing ink prepared from a non-water-soluble degradable polymer with good biocompatibility on the surface of the regenerated chitosan/polyvinyl alcohol film through 3D printing.
Further, the double-layer film of the invention is characterized in that the water-insoluble degradable polymer is any one of polycaprolactone, polylactic acid, polydioxanone or a copolymer of polycaprolactone and polylactic acid.
Meanwhile, the invention also provides a preparation method of the double-layer film, which comprises the following steps:
1) Preparation of printing ink a: adding chitosan and a solvent in a mass percent of 1-3% into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 40-60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 5-10% polyvinyl alcohol aqueous solution by mass percent; mixing the regenerated chitosan homogeneous phase solution with a polyvinyl alcohol aqueous solution according to the mass percentage of 10-20% to obtain a homogeneous phase solution A; then, adding a precipitator into the homogeneous phase solution A, wherein the mass percentage of the precipitator to the homogeneous phase solution A is 100-200%, obtaining white floccule, and filtering and drying to obtain printing ink A;
2) Preparation of printing ink B: the photoinitiator, the photocrosslinking agent and the ethanol are mixed according to the mass ratio of 0.1-0.3: 0.1 to 0.3: 40-60 to obtain a homogeneous solution B; and then adding a water-insoluble degradable polymer into the homogeneous solution B, wherein the mass ratio of the water-insoluble degradable polymer to the homogeneous solution B is 8-12: 1-3, quickly stirring, and obtaining printing ink B after ethanol volatilizes;
3) Preparing a double-layer film: respectively adding the printing ink A and the printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 100-120 ℃ and the printing pressure of 600-800 kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2-0.4 mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the regenerated chitosan/polyvinyl alcohol film by using printing ink B at the printing temperature of 90-140 ℃ and the printing pressure of 600-900 kPa, and simultaneously turning on an ultraviolet lamp to ensure that the ultraviolet wavelength is 365nm; and adjusting the number of layers of 3D printing to obtain the water-insoluble degradable polymer film with the thickness of 0.4-0.6 mm, and finally preparing the double-layer film.
Further, the preparation method of the double-layer film of the invention comprises the following steps:
in the step 1), the solvent is at least one of dilute acetic acid, dilute malic acid and dilute ascorbic acid. The precipitant is one of sodium hydroxide, magnesium hydroxide and sodium bicarbonate.
In the step 2), the photoinitiator is one of benzophenone, methylbenzophenone and phenyl benzophenone. The photocrosslinking agent is one of triallyl isocyanurate, trimethallyl isocyanate and triallyl isocyanate.
In the step 2), when the mixture is rapidly stirred, the stirring speed is 500-1000 rpm, and the stirring temperature is 20-30 ℃.
The double-layer film prepared by the invention is self-curled into a small tissue engineering blood vessel in a liquid environment or is further prepared into a blood vessel stent with a self-expansion function in the liquid environment; wherein the liquid is one of water, simulated body fluid and phosphate buffer solution. The concrete application is as follows:
the application of the double-layer film in preparing the small tissue engineering blood vessel is as follows: the double-layer film with the thickness of 0.4-0.8 mm is adopted and is a plane double-layer film at normal temperature and in a natural state, the double-layer film is placed in a liquid environment, and is stimulated to self-curl into a tubular object with the inner diameter of 4.0-6.0 mm and the wall thickness of 0.4-0.8 mm by the liquid environment.
The application of the double-layer film in preparing the vascular stent with the self-expanding function is as follows: the self-curling tubular object is placed in a liquid environment, the inner diameter of the expanded tubular object is 8.0-10.0 mm under the stimulation of the liquid environment, and the wall thickness is basically unchanged.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention can obtain intelligent films with different thicknesses and sizes by 3D printing according to requirements.
(2) The intelligent film can rapidly obtain the tissue engineering small blood vessel or the blood vessel stent with the required size according to the requirement so as to meet the clinical requirement under the emergency condition.
(3) The intelligent film can respond to liquid environment, and greatly facilitates application of the intelligent film in a human body.
Drawings
FIG. 1 is a schematic diagram of the self-curling and self-expanding process of a bilayer film.
FIG. 2 is a photomicrograph of a bilayer film self-curling (a) and self-expanding (b);
fig. 3 is a graph of the hemolysis rates of commercial expanded polytetrafluoroethylene (ePTFE), polycaprolactone, and regenerated chitosan/polyvinyl alcohol, where NS indicates no statistical difference (not significant), p-value <0.05, which is a parameter statistically used to determine the results of the hypothesis test, and p-value <0.05 indicates significant statistical difference.
FIG. 4 is a photograph of live and dead staining of endothelial cells cultured on the surfaces of polycaprolactone and regenerated chitosan/polyvinyl alcohol for 1, 3 and 5 days, respectively, for example 1.
Detailed Description
The invention provides a double-layer film for a tissue engineering small blood vessel or a blood vessel stent, which is prepared by respectively carrying out 3D printing on two kinds of printing ink (respectively a water-insoluble degradable polymer with good biocompatibility and chitosan/polyvinyl alcohol), namely, firstly preparing a regenerated chitosan/polyvinyl alcohol film, and then preparing a water-insoluble degradable polymer film with the thickness of 0.4-0.6 mm on the surface of the regenerated chitosan/polyvinyl alcohol film. Wherein the water-insoluble degradable polymer is any one of polycaprolactone, polylactic acid, polydioxanone or copolymers thereof. The preparation steps of the double-layer film are as follows:
(1) Preparation of printing ink a: adding chitosan and a solvent in a mass percent of 1-3% into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 40-60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 5-10% polyvinyl alcohol aqueous solution by mass percent; mixing the regenerated chitosan homogeneous solution with a polyvinyl alcohol aqueous solution according to the mass percent of 10-20% to obtain a homogeneous solution A; then, mixing the homogeneous solution with 40-60% of precipitator by mass percent to obtain white floccule, and filtering and drying to obtain printing ink A; wherein the solvent is at least one of dilute acetic acid, dilute malic acid, and dilute ascorbic acid, and the precipitant is any one of sodium hydroxide, magnesium hydroxide, and sodium bicarbonate
(2) Preparation of printing ink B: the photoinitiator, the photocrosslinking agent and the ethanol are mixed according to the mass ratio of 0.1-0.3: 0.1 to 0.3: 40-60 to obtain homogeneous solution B; and then adding a water-insoluble degradable polymer into the homogeneous solution B, wherein the mass ratio of the water-insoluble degradable polymer to the homogeneous solution B is 8-12: 1-3, rapidly stirring at the stirring speed of 500-1000 rpm and the stirring temperature of 20-30 ℃, and obtaining printing ink B after ethanol volatilizes; wherein the photoinitiator is any one of benzophenone, methyl benzophenone and phenyl benzophenone. The photocrosslinking agent is any one of triallyl isocyanurate, trimethallyl isocyanate and triallyl isocyanate.
(3) Preparing a double-layer film: respectively adding the printing ink A and the printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 100-120 ℃ and the printing pressure of 600-800 kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2-0.4 mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the regenerated chitosan/polyvinyl alcohol film by using printing ink B at the printing temperature of 90-140 ℃ and the printing pressure of 600-900 kPa, and simultaneously turning on an ultraviolet lamp to enable the ultraviolet wavelength to be 365nm; and adjusting the number of layers of 3D printing to obtain the water-insoluble degradable polymer film with the thickness of 0.4-0.6 mm, and finally preparing the double-layer film.
The chitosan/polyvinyl alcohol in the double-layer film can generate self-curling behavior through stimulation of a liquid environment, wherein the liquid environment is any one of water, simulated body fluid and phosphate buffer solution. The double-layer film prepared in the above way can be self-curled into a small tissue engineering blood vessel in a liquid environment or further made into a blood vessel stent with a self-expansion function in a liquid environment according to requirements, as shown in fig. 1. The planar double-layer film with the thickness of 0.4-0.8 mm prepared by the invention is stimulated to self-curl by a liquid environment to form a tubular object with the inner diameter of 4.0-6.0 mm and the wall thickness of 0.4-0.8 mm, and the tubular object is used as a tissue engineering small vessel stent. The tubular object with the inner diameter of 4.0-6.0 mm and the wall thickness of 0.4-0.8 mm is prepared into a self-expanding vascular stent, and the inner diameter of the tubular object can be expanded to 8.0-10.0 mm by further stimulation of the liquid environment.
While the present invention will be described in detail and with reference to the accompanying drawings and specific embodiments thereof, it should be understood that the present invention is not limited to the embodiments shown herein, but is capable of other insubstantial modifications and variations within the scope of the invention as shown and described herein.
Example 1
Adding 1.5g of chitosan, 2g of acetic acid and 96.5g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 8% polyvinyl alcohol aqueous solution by mass, and mixing 15g of regenerated chitosan homogeneous solution with 85g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous solution; subsequently, 100g of sodium hydroxide was added to the homogeneous solution to obtain a white floc, which was then filtered and dried to obtain printing ink a.
Adding 0.2g of benzophenone, 0.2g of triallyl isocyanurate and 50ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous phase solution, then adding 6g of polycaprolactone, rapidly stirring at the stirring speed of 400rpm and the temperature of 26 ℃, and obtaining the printing ink B after the ethanol is volatilized.
Respectively adding 2g of printing ink A and 2g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 100 ℃ and the printing pressure of 800kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.4mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the chitosan/polyvinyl alcohol layer by using printing ink B at the printing temperature of 90 ℃ and the printing pressure of 800kPa, and simultaneously turning on an ultraviolet lamp to obtain the ultraviolet wavelength of 365nm; and adjusting the number of layers of 3D printing to obtain a polycaprolactone film with the thickness of 0.2mm on the regenerated chitosan/polyvinyl alcohol film, and finally obtaining a double-layer film formed by compounding polycaprolactone and regenerated chitosan/polyvinyl alcohol.
Example 2
Adding 2g of chitosan, 2g of acetic acid and 96g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 10% polyvinyl alcohol aqueous solution, and mixing 15g of regenerated chitosan homogeneous solution with 85g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous solution; subsequently, 100g of sodium hydroxide precipitant was added to the homogeneous solution to obtain a white floc, which was then filtered and dried to obtain printing ink a.
Adding 0.1g of benzophenone, 0.1g of triallyl isocyanurate and 40ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous solution, then adding 6g of polydioxanone, rapidly stirring, and volatilizing the ethanol to obtain printing ink B, wherein the stirring speed is 400rpm, and the temperature is 28 ℃.
Respectively adding 3g of printing ink A and 1g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 110 ℃ and the printing pressure of 800kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.6mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the chitosan/polyvinyl alcohol layer by using printing ink B at the printing temperature of 110 ℃ and the printing pressure of 800kPa, and simultaneously turning on an ultraviolet lamp with the ultraviolet wavelength of 365nm; and (3) adjusting the number of layers of 3D printing to obtain a poly (p-dioxanone) film with the thickness of 0.2mm on the regenerated chitosan/polyvinyl alcohol film, and finally obtaining a double-layer film compounded by the poly (p-dioxanone) and the regenerated chitosan/polyvinyl alcohol.
Example 3
Adding 1g of chitosan, 1g of acetic acid and 98g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 8% polyvinyl alcohol aqueous solution, and mixing 20g of regenerated chitosan homogeneous solution with 80g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous solution; subsequently, 100g of sodium hydroxide precipitant was added to the homogeneous solution to obtain a white floc, which was then filtered and dried to obtain printing ink a.
Adding 0.2g of benzophenone, 0.2g of triallyl isocyanurate and 50ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous phase solution, then adding 10g of polycaprolactone/poly (p-dioxanone) copolymer, quickly stirring, and obtaining printing ink B after ethanol is volatilized, wherein the stirring speed is 500rpm, and the temperature is 28 ℃.
Respectively adding 2g of printing ink A and 2g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 110 ℃ and the printing pressure of 800kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.4mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the chitosan/polyvinyl alcohol layer by using printing ink B at the printing temperature of 100 ℃ and the printing pressure of 800kPa, and simultaneously turning on an ultraviolet lamp with the ultraviolet wavelength of 365nm; and adjusting the number of layers of 3D printing to obtain a polycaprolactone/poly (p-dioxanone) copolymer film with the thickness of 0.4mm, and finally obtaining a double-layer film compounded by polycaprolactone/poly (p-dioxanone) copolymer and regenerated chitosan/polyvinyl alcohol.
Example 4
Adding 2g of chitosan, 2g of malic acid and 96g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 8% polyvinyl alcohol aqueous solution, and mixing 15g of regenerated chitosan homogeneous solution with 85g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous solution; subsequently, 100g of sodium hydroxide precipitant was added to the homogeneous solution to obtain a white floc, which was then filtered and dried to obtain printing ink a.
Adding 0.2g of benzophenone, 0.2g of triallyl isocyanurate and 50ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous solution, then adding 10g of polylactic acid/polycaprolactone copolymer, quickly stirring, and obtaining printing ink B after ethanol is volatilized, wherein the stirring speed is 400rpm, and the temperature is 28 ℃.
Respectively adding 2g of printing ink A and 2g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 100 ℃ and the printing pressure of 700kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2mm by adjusting the number of layers of 3D printing; printing on the surface of the chitosan/polyvinyl alcohol layer by using printing ink B at the printing temperature of 110 ℃ and the printing pressure of 800kPa, and simultaneously turning on an ultraviolet lamp to obtain the ultraviolet wavelength of 365nm; the number of layers of 3D printing is adjusted to obtain the polylactic acid/polycaprolactone copolymer film with the thickness of 0.6mm, and finally the double-layer film formed by compounding the polylactic acid/polycaprolactone copolymer and the regenerated chitosan/polyvinyl alcohol is obtained
Example 5
Adding 2g of chitosan, 2g of malic acid and 96g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 10% polyvinyl alcohol aqueous solution, and mixing 15g of regenerated chitosan homogeneous phase solution with 85g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous phase solution; subsequently, 100g of sodium hydroxide precipitant was added to the homogeneous solution to obtain a white floc, which was then filtered and dried to obtain printing ink a.
Adding 0.2g of benzophenone, 0.2g of triallyl isocyanurate and 50ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous solution, then adding 10g of polylactic acid/polydioxanone copolymer, quickly stirring, and volatilizing the ethanol to obtain printing ink B, wherein the stirring speed is 400rpm, and the temperature is 28 ℃.
Respectively adding 2g of printing ink A and 2g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 110 ℃ and the printing pressure of 700kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.4mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the chitosan/polyvinyl alcohol layer by using the printing ink B at the printing temperature of 140 ℃ and the printing pressure of 900kPa, and simultaneously turning on an ultraviolet lamp with the ultraviolet wavelength of 365nm; and (3) adjusting the number of layers of 3D printing to obtain a polylactic acid/poly (p-dioxanone) copolymer film with the thickness of 0.4mm, and finally preparing a double-layer film compounded by the polylactic acid/poly (p-dioxanone) copolymer and regenerated chitosan/polyvinyl alcohol.
Example 6
Adding 2.5g of chitosan, 2g of malic acid and 95.5g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 5% polyvinyl alcohol aqueous solution, and mixing 10g of regenerated chitosan homogeneous solution with 90g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous solution; subsequently, 150g of sodium hydroxide precipitant was added to the homogeneous solution to obtain a white floc, which was then filtered and dried to obtain printing ink a.
Adding 0.2g of benzophenone, 0.2g of triallyl isocyanurate and 50ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous solution, then adding 10g of polycaprolactone, quickly stirring, and obtaining printing ink B after the ethanol is volatilized, wherein the stirring speed is 400rpm, and the temperature is 28 ℃.
Respectively adding 2g of printing ink A and 2g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 110 ℃ and the printing pressure of 700kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.4mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the chitosan/polyvinyl alcohol layer by using printing ink B at the printing temperature of 100 ℃ and the printing pressure of 800kPa, and simultaneously turning on an ultraviolet lamp with the ultraviolet wavelength of 365nm; and (3) adjusting the number of layers of 3D printing to obtain a polycaprolactone film with the thickness of 0.4mm, and finally preparing a double-layer film formed by compounding polycaprolactone and regenerated chitosan/polyvinyl alcohol.
Example 7
Adding 3g of chitosan, 3g of acetic acid and 94g of ultrapure water into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 6% polyvinyl alcohol aqueous solution, and mixing 10g of regenerated chitosan homogeneous solution with 90g of polyvinyl alcohol aqueous solution to prepare regenerated chitosan/polyvinyl alcohol homogeneous solution; subsequently, 200g of a sodium hydroxide precipitant was added to the homogeneous solution to obtain a white floc, which was filtered and dried to obtain a printing ink a.
Adding 0.2g of benzophenone, 0.2g of triallyl isocyanurate and 50ml of ethanol into a dissolving kettle, uniformly mixing to obtain a homogeneous solution, then adding 10g of polylactic acid/polydioxanone copolymer, quickly stirring, and obtaining printing ink B after ethanol is volatilized, wherein the stirring speed is 400rpm, and the temperature is 28 ℃.
Respectively adding 2g of printing ink A and 2g of printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 110 ℃ and the printing pressure of 700kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.4mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the chitosan/polyvinyl alcohol layer by using the printing ink B at the printing temperature of 140 ℃ and the printing pressure of 900kPa, and simultaneously turning on an ultraviolet lamp with the ultraviolet wavelength of 365nm; and (3) adjusting the number of layers of 3D printing to obtain a polylactic acid/poly (p-dioxanone) copolymer film with the thickness of 0.4mm, and finally preparing a double-layer film compounded by the polylactic acid/poly (p-dioxanone) copolymer and the regenerated chitosan/polyvinyl alcohol.
Research materials
Fig. 1 is a schematic diagram of the self-curling and self-expanding process of a double-layer film for a tissue engineering small vessel or a vessel stent prepared by the invention, wherein a regenerated chitosan/polyvinyl alcohol film is arranged at the position of reference numeral 1, and a water-insoluble degradable polymer film is arranged at the position of reference numeral 2. The double-layer film can be stimulated by a liquid environment to be self-curled into small tissue engineering blood vessels, and can also be self-curled into a tubular shape by the plane film so as to be implanted into a body as a blood vessel stent.
(1) Self-curling and expanding under stimulation of liquid environment
A bilayer film as described in example 1, which exhibited more pronounced self-curling and self-expanding behavior upon stimulation with water, as shown in fig. 2, wherein (a) is a macroscopic photograph of the self-curling of the bilayer film prepared in example 1, scale: 10mm; (b) Is a macro photograph of the self-curled film shown in (a) and then self-expanded, with a scale: 10mm. The double-layer film is a plane double-layer film (20 multiplied by 20 mm) before self-curling, and the diameter after self-curling is 5mm; in the self-expanding process, the diameter before self-expansion is 6mm, and the diameter after self-expansion is 8mm.
(2) Blood compatibility
Whether the small vessels or the vascular stents of tissue engineering need to be evaluated for the blood compatibility, generally, the hemolysis rate of less than 5 percent means that the damage to red blood cells is small and the blood compatibility is better. The double-layer film prepared in example 1 was subjected to a hemolysis rate test, and fresh anticoagulated rabbit blood was selected as blood. As can be seen from FIG. 3, the hemolysis rate of polycaprolactone is 0.38 + -0.04%, the hemolysis rate of regenerated chitosan/polyvinyl alcohol is 0.41 + -0.06%, and the hemolysis rate is lower than that of commercial artificial vascular expanded polytetrafluoroethylene (ePTFE) by 0.62 + -0.06%, which indicates that the double-layer film has good blood compatibility. Examples 2-7 were also tested for hemolysis rate and the results are shown in Table 1.
TABLE 1
(3) Biocompatibility
Endothelial cells are the most important cell type in vascular tissue and therefore, endothelial cells were selected for analysis of the biocompatibility of the bilayer membrane. For the bilayer films prepared in example 1, fig. 4 shows the live-dead staining photographs of endothelial cells cultured on the polycaprolactone and regenerated chitosan/polyvinyl alcohol surfaces for 1, 3 and 5 days, scale: 100 μm. As can be seen from FIG. 4, the endothelial cells proliferated faster on the surfaces of the polycaprolactone and the regenerated chitosan/polyvinyl alcohol material, and spread more on day 3, and the proliferation condition was better as the culture time was longer, which indicates that the selected material has good cell compatibility and can be endothelialized rapidly.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than restrictive, and many changes may be made by one skilled in the art in light of the above teachings without departing from the spirit of the present invention and these are intended to be within the scope of the present invention.
Claims (10)
1. A double-layer film for a tissue engineering small blood vessel or a blood vessel stent is characterized in that the double-layer film is prepared by 3D printing, one layer is a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2-0.4 mm prepared by printing ink configured by chitosan/polyvinyl alcohol through 3D printing, and the other layer is a non-water-soluble degradable polymer film with the thickness of 0.4-0.6 mm prepared by printing ink configured by a non-water-soluble degradable polymer with good biocompatibility through 3D printing on the surface of the regenerated chitosan/polyvinyl alcohol film.
2. The bilayer film of claim 1, wherein said water-insoluble degradable polymer is any one of polycaprolactone, polylactic acid, polydioxanone or their copolymers.
3. A method for preparing the bilayer film of claim 1 comprising the steps of:
1) Preparation of printing ink a:
adding chitosan and a solvent in a mass percent of 1-3% into a dissolving kettle with a thermometer, and stirring and dissolving at the temperature of 40-60 ℃ to obtain a regenerated chitosan homogeneous phase solution; preparing 5-10% polyvinyl alcohol aqueous solution by mass percent; mixing the regenerated chitosan homogeneous solution with a polyvinyl alcohol aqueous solution according to the mass percent of 10-20% to obtain a homogeneous solution A;
then, adding a precipitator into the homogeneous phase solution A, wherein the mass percentage of the precipitator to the homogeneous phase solution A is 100-200%, obtaining white floccule, and filtering and drying to obtain printing ink A;
2) Preparation of printing ink B:
the photoinitiator, the photocrosslinking agent and the ethanol are mixed according to the mass ratio of 0.1-0.3: 0.1 to 0.3: 40-60 to obtain a homogeneous solution B; and then adding a water-insoluble degradable polymer into the homogeneous solution B, wherein the mass ratio of the water-insoluble degradable polymer to the homogeneous solution B is 8-12: 1-3, quickly stirring, and volatilizing ethanol to obtain printing ink B;
3) Preparing a double-layer film:
respectively adding the printing ink A and the printing ink B into two material cylinders of a 3D printer for preheating; printing by using the printing ink A at the printing temperature of 100-120 ℃ and the printing pressure of 600-800 kPa, and obtaining a regenerated chitosan/polyvinyl alcohol film with the thickness of 0.2-0.4 mm by adjusting the number of layers of 3D printing; continuously printing on the surface of the regenerated chitosan/polyvinyl alcohol film by using printing ink B at the printing temperature of 90-140 ℃ and the printing pressure of 600-900 kPa, and simultaneously turning on an ultraviolet lamp to enable the ultraviolet wavelength to be 365nm; and adjusting the number of layers of 3D printing to obtain the water-insoluble degradable polymer film with the thickness of 0.4-0.6 mm, and finally preparing the double-layer film.
4. The method for preparing a bilayer film according to claim 3, wherein in step 1), the solvent is one of dilute acetic acid, dilute malic acid, and dilute ascorbic acid; the precipitant is one of sodium hydroxide, magnesium hydroxide and sodium bicarbonate.
5. The method for preparing a double-layered film according to claim 3, wherein the stirring speed is 500 to 1000rpm and the stirring temperature is 20 to 30 ℃ during the rapid stirring in the step 2).
6. The method for preparing a two-layer film according to claim 3, wherein in step 2), the photoinitiator is one of benzophenone, methylbenzophenone and phenylbenzophenone, and the photocrosslinking agent is one of triallyl isocyanurate, trimethallyl isocyanate and triallyl isocyanate.
7. Use of the bilayer membrane of claim 1 or 2 prepared by any of the preparation methods of claims 3 to 6, wherein the bilayer membrane is self-curled into a small tissue engineering vessel in a liquid environment or further prepared into a vessel stent with self-expanding function in a liquid environment.
8. The use of the bilayer membrane of claim 7, wherein the liquid is one of water, simulated body fluid, phosphate buffered saline.
9. The use of the double-layered film according to claim 8, wherein a double-layered film having a thickness of 0.4 to 0.8mm is used, the double-layered film is a planar double-layered film in a natural state at room temperature, the double-layered film is placed in a liquid environment, and the double-layered film is self-curled into a tubular object having an inner diameter of 4.0 to 6.0mm and a wall thickness of 0.4 to 0.8mm by stimulation of the liquid environment.
10. The use of a bilayer membrane according to claim 9 wherein the tube is exposed to a fluid environment and has an expanded inner diameter of 8.0 to 10.0mm and a constant wall thickness when exposed to the fluid environment.
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