CN110396205B - Pickering high internal phase emulsion, 3D printing porous scaffold material and preparation method thereof - Google Patents

Pickering high internal phase emulsion, 3D printing porous scaffold material and preparation method thereof Download PDF

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CN110396205B
CN110396205B CN201910621012.9A CN201910621012A CN110396205B CN 110396205 B CN110396205 B CN 110396205B CN 201910621012 A CN201910621012 A CN 201910621012A CN 110396205 B CN110396205 B CN 110396205B
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emulsion
high internal
printing
internal phase
water
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CN110396205A (en
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周武艺
刘水凤
李奕恒
胡洋
张坚诚
董先明
鲍思奇
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Guangzhou Trauer Biotechnology Co ltd
South China Agricultural University
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Guangzhou Trauer Biotechnology Co ltd
South China Agricultural University
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Abstract

The invention relates to a Pickering high internal phase emulsion, a 3D printing porous scaffold material prepared from the Pickering high internal phase emulsion and a preparation method of the Pickering high internal phase emulsion. According to the invention, nano hydroxyapatite particles are used as an emulsion stabilizer, gelatin, collagen and genipin are dissolved in deionized water to form a continuous phase of the emulsion, an organic solvent is used as a disperse phase, an oil-in-water Pickering high internal phase emulsion is formed through emulsification treatment and crosslinking reaction, so that the continuous phase of the emulsion is fixed, and finally, after a gel scaffold is obtained through 3D printing, the solvent is volatilized to remove the disperse phase and is dried to obtain the porous scaffold material with interconnected pores and adjustable pore diameter. The porous scaffold material prepared by adopting an emulsion template method and combining a 3D printing technology has the advantages of high porosity, inter-pore communication, adjustable pore diameter, good biocompatibility, no toxicity or harm to organisms and the like, and has wide application prospect in the field of biomedical materials.

Description

Pickering high internal phase emulsion, 3D printing porous scaffold material and preparation method thereof
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to a Pickering high internal phase emulsion, a 3D printing porous scaffold material prepared from the Pickering high internal phase emulsion and a preparation method of the 3D printing porous scaffold material.
Background
The porous scaffold material is a material with a three-dimensional network structure, contains a large number of gaps inside, and has the characteristics of unique large specific surface area, low density, high porosity and the like, so that the porous scaffold material has very wide application in the field of biomedicine, particularly in the field of tissue engineering. Therefore, it is highly desirable to construct a porous scaffold material suitable for use in tissue repair. An ideal porous scaffold material for tissue repair should have the following characteristics: good mechanical properties to withstand environmental stresses, no cellular toxicity, good biocompatibility, drug loading, sustained release and high porosity to ensure transport of cellular nutrients and metabolic waste.
At present, although porous scaffold materials can be prepared by methods for preparing biological porous scaffold materials, such as a phase separation method, a foaming method, a pore-forming agent method, a solvent casting method and the like, the connectivity between adjacent pores of the materials is poor, the pore diameter is difficult to control, and the degradation speed of the materials in a living body is slow, so that the application of the materials in the field of tissue engineering is greatly limited. Recently, it has become a unique preparation technology to prepare porous scaffold materials with rich pore channel structures by using High Internal Phase Emulsions (HIPEs) as templates. The high internal phase emulsion is an emulsion with the internal phase volume fraction higher than 74 percent, the external phase polymerization and solidification are initiated by taking the internal phase as a template, and the template is removed by simple solvent evaporation, so that the macroporous support material with interconnected pore channel structure, high porosity and low density can be prepared.
Most of the traditional stabilizers of the high internal phase emulsion are surfactants, and the traditional high internal phase emulsion has the disadvantages of large dosage, high toxicity, high side effect, poor stability and unrecyclable property in the preparation process, thereby being very unfavorable for the application in the field of biomedical materials. Therefore, in recent years, a method of stabilizing an emulsion by replacing a surfactant with amphiphilic solid nanoparticles and microparticles has attracted attention, and such a high internal phase emulsion stabilized with solid particles is called a Pickering emulsion. Compared with the traditional surfactant for stabilizing the high internal phase emulsion, the solid particles used as the emulsion stabilizer not only have small dosage and can avoid the cytotoxicity of the surfactant, but also have the advantages of irreversible interface particle self-assembly performance, high stability, excellent mechanical property and the like, and are very suitable for the field of biomedical materials.
Chinese patent CN105968402A discloses a preparation method by using Pickering high internal phase emulsion as a template
Although the porous scaffold material prepared by the method has good biocompatibility and good mechanical property, polyacrylamide is difficult to degrade, the porous scaffold material based on polyacrylamide needs to be removed through a secondary operation after being introduced into a human body, so that secondary damage to the human body can be caused, and in addition, the acrylamide product obtained after partial degradation of polyacrylamide has toxicity and is harmful to the nervous system of an organism. Chinese patent CN108201636A discloses a preparation method of a natural polymer-based 3D porous composite scaffold with controllable pore size, wherein a Pickering emulsion template method is adopted, aminated gelatin nanoparticles are used as a stabilizer, natural polymers are used as base materials, and the 3D porous composite scaffold with controllable pore size is prepared; in addition, during the preparation of aminated gelatin nanoparticles, residual acetone may remain during subsequent processing, which is harmful to living organisms. Chinese patent CN107362392A discloses a nano-hydroxyapatite/carboxymethyl chitosan/polylactic acid glycolic acid micro-nano hybrid drug-loaded scaffold and a bionic preparation method thereof, wherein the method takes nano-hydroxyapatite and carboxymethyl chitosan as water phases as emulsion continuous phases; taking a dichloromethane solution of polylactic glycolic acid as an oil phase as an emulsion dispersion phase; the preparation method comprises the steps of fixing carboxymethyl chitosan in a continuous phase by using glutaraldehyde as a cross-linking agent, using icariin as a carrier drug, and preparing the three-dimensional bionic hybrid drug-carrying scaffold for bone repair by using a high-speed emulsifying machine in combination with solvent evaporation and freeze drying technologies.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a Pickering high internal phase emulsion, a 3D printing porous scaffold material prepared from the Pickering high internal phase emulsion and a preparation method of the porous scaffold material.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a Pickering high internal phase emulsion is designed, which comprises an aqueous phase part and an oil phase part, wherein the aqueous phase part comprises water and 0.5-5.0g of gelatin, 0.4-0.8g of collagen, 0.01-0.05g of genipin and 0.8-1.5g of hydroxyapatite contained in each 3.0m of L water, and the oil phase part comprises dichloromethane and 0.06-1.02g of polycaprolactone (PC L) contained in each 10m of L dichloromethane.
Preferably, the volume ratio between the aqueous phase part and the oil phase part is (2-4): 10, more preferably 3: 10.
Preferably, the oil phase portion contains 0.1-0.8g of polycaprolactone per 10m L of methylene chloride.
Preferably, the water phase part contains 1.0-3.0g of gelatin, 0.5-0.7g of collagen, 0.02-0.04g of genipin and 1.02-1.20g of hydroxyapatite in each 3m of L m of water.
Preferably, the hydroxyapatite is nano hydroxyapatite.
The preparation method of the Pickering high internal phase emulsion comprises the following steps: dispersing the polycaprolactone into dichloromethane, and forming an oil phase part after uniform dispersion; dispersing the gelatin, the collagen, the genipin and the hydroxyapatite into water, and forming a water phase part after uniform dispersion; and mixing and dispersing the oil phase part and the water phase part uniformly, and standing for crosslinking reaction to form an oil-in-water Pickering high internal phase emulsion for later use.
The 3D printing porous scaffold material is designed and prepared by printing the Pickering high internal phase emulsion, and specifically comprises the following steps: and (3) introducing the Pickering high internal phase emulsion into a 3D printer, printing according to a set model to obtain a 3D printing support material, and drying.
The invention has the beneficial effects that:
(1) the invention adopts nano hydroxyapatite (Ca)10(PO4)6(OH)2HAP for short) as the stabilizer of Pickering emulsion, has chemical composition and structure similar to the components of bones and teeth of organisms, has no toxicity, harm and carcinogenesis to the organisms, has good biocompatibility and bioactivity, and has good osteoconductivity, biocompatibility and bioactivity in the organisms. Moreover, the added hydroxyapatite particles can lead the mechanical property of the bracket to be betterBecause more stress is transferred from the PC L matrix to the rigid hydroxyapatite particles when the scaffold is stressed, the mechanical properties of the scaffold are enhanced.
(2) As can be seen from the attached figures 1, 2, 3 and 4, the porous scaffold prepared by different PC L contents has the advantages that as the content of PC L is increased, the pore diameter and the pore throat size of the porous scaffold are both reduced, the pore wall thickness of the scaffold is increased, and the pore structure is more and more complete, because the emulsion prepared under higher concentration of PC L has thicker polymer film between adjacent emulsion droplets, increased viscosity of the pore wall and increased stability of the emulsion, the pore diameter and the pore throat size are reduced and the thickness of the pore wall is increased after the solvent is evaporated.
(3) The 3D printing porous scaffold material has large pore structures which are very closely arranged, as can be seen from an electron microscope image, the pore diameters of most of pores fall within the interval of 10-20 mu m, and the pores are communicated with one another, so that the structure is very favorable for cell adhesion and proliferation in organisms, is favorable for transportation of nutrient substances and metabolic wastes, and has great application value in the field of biomedicine.
(4) The porous scaffold material is prepared by combining the high internal phase emulsion with the 3D printing technology, the scaffold material with different shapes and sizes can be prepared according to the actual application requirements, raw materials can be saved in specific application, and personalized customization can be realized.
(5) The invention adopts the natural biological cross-linking agent genipin to carry out cross-linking reaction on the collagen and the gelatin, improves the mechanical property of the material, and does not generate substances harmful to organisms.
(6) According to the invention, after the Pickering high internal phase emulsion is directly prepared, the 3D printing is carried out to obtain the stent material, the operation steps are simple, the preparation process is simple and easy to implement, the conditions are mild, the production period is short, and the application and popularization values are relatively high.
Drawings
FIG. 1 is an SEM image of a cross-section of a porous scaffold material printed in example 13D.
FIG. 2 is an SEM image of a cross-section of a porous scaffold material printed in example 23D.
FIG. 3 is an SEM image of a cross-section of a porous scaffold material printed in example 33D.
FIG. 4 is an SEM image of a cross-section of example 43D printed porous scaffold material.
Detailed Description
The present invention is described in further detail below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.1 g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.08g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the volume ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
Example 2
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.2 g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.08g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the volume ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
Example 3
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.4 g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.08g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the volume ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
Example 4
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.8g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.08g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the volume ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
Example 5
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.8g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.02g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
Example 6
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.8g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.14g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the volume ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
Example 7
A method for preparing a 3D printing porous scaffold material by using Pickering high internal phase emulsion comprises the following steps:
(1) weighing 0.8g of polycaprolactone (PC L) into 10 ml of dichloromethane, magnetically stirring and dispersing for 30min at normal temperature to form an oil phase part, weighing 1.5g of gelatin, 0.6g of collagen, 0.03g of genipin and 1.20g of hydroxyapatite into 3m L of deionized water, stirring and dispersing for 30min at normal temperature to form a water phase part, weighing the oil phase part by using a pipette, adding the oil phase part into the water phase part (the volume ratio of the water phase part to the oil phase part is 3: 10), shaking for 10 min by using a vortex mixer, standing for crosslinking reaction for 24 h to form an oil-in-water emulsion for later use.
(2) Introducing the oil-in-water emulsion obtained in the step (1) after 24 hours of crosslinking reaction into an injector of a 3D printer, starting printing according to a set model, and obtaining a 3D printing support material after printing; and then carrying out freeze drying treatment on the obtained 3D printing support material for 24 hours to obtain the 3D printing porous support material prepared from the Pickering high internal phase emulsion.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as effective replacements within the protection scope of the present invention.

Claims (6)

1. A Pickering high internal phase emulsion comprises an aqueous phase part and an oil phase part, and is characterized in that the aqueous phase part comprises water and 0.5-5.0g of gelatin, 0.4-0.8g of collagen, 0.01-0.05g of genipin and 0.8-1.5g of hydroxyapatite contained in each 3.0m L of water, the oil phase part comprises dichloromethane and 0.06-1.02g of polycaprolactone contained in each 10m L of dichloromethane, and the volume ratio of the aqueous phase part to the oil phase part is (2-3): 10;
the Pickering high internal phase emulsion is made by a process comprising the steps of: dispersing the polycaprolactone into dichloromethane, and forming an oil phase part after uniform dispersion; dispersing the gelatin, the collagen, the genipin and the hydroxyapatite into water, and forming a water phase part after uniform dispersion; and mixing and dispersing the oil phase part and the water phase part uniformly, and standing for crosslinking reaction to form the oil-in-water Pickering high internal phase emulsion.
2. The Pickering high internal phase emulsion of claim 1, wherein: the volume ratio between the aqueous phase portion and the oil phase portion was 3: 10.
3. The Pickering high internal phase emulsion of claim 1, wherein the oil phase portion comprises 0.1-0.8g polycaprolactone per 10m L methylene chloride.
4. The Pickering high internal phase emulsion according to claim 1, wherein the aqueous phase portion comprises 1.0-3.0g of gelatin, 0.5-0.7g of collagen, 0.02-0.04g of genipin and 1.02-1.20g of hydroxyapatite per 3m of L water.
5. The Pickering high internal phase emulsion of claim 1, wherein: the hydroxyapatite is nano hydroxyapatite.
6. A3D printing porous scaffold material prepared by printing the Pickering high internal phase emulsion of any one of claims 1-5, which comprises the following steps: and (3) introducing the Pickering high internal phase emulsion into a 3D printer, printing according to a set model to obtain a 3D printing support material, and drying.
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