CN115025284B - Graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological scaffold and preparation method thereof - Google Patents
Graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological scaffold and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological scaffold and a preparation method thereof, comprising the following steps: growth of piezoelectric material BaTiO on GO sheets by hydrothermal reaction 3 Obtaining BaTiO 3 -GO powder; baTiO is mixed with 3 Dispersing GO and PLGA in ethanol, stirring, centrifuging, and drying to obtain BaTiO 3 -GO/PLGA composite powder; baTiO production by additive manufacturing technique 3 -GO/PLGA bioscaffold. The invention aims to solve the problem that the PLGA stent is directly introduced into BaTiO 3 When BaTiO 3 There is a problem that lattice distortion is caused by oxygen vacancies to deteriorate piezoelectric characteristics, and BaTiO is healed by oxygen-containing functional groups of GO 3 Oxygen vacancy defects of BaTiO are promoted 3 To improve the polarization ability of BaTiO 3 Piezoelectric properties of GO in PLGA scaffolds. Additional advantages are: GO and BaTiO 3 The PLGA stent is more beneficial to the adhesion growth of cells due to the good hydrophilic property; in the hydrothermal reaction, a conduction path is formed by the reduced graphene oxide grid, so that effective transmission of charges is promoted, and an output voltage signal of the biological scaffold is improved; baTiO 3 The GO nano-sheets are used as bridging to improve the mechanical strength of the PLGA stent.
Description
Technical Field
The invention relates to the field of 3D printing composite stents, in particular to a graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological stent with piezoelectric stimulation and a preparation method thereof, and belongs to the technical field of biological stent preparation.
Background
With aging population, traffic accident rate and increasing incidence of diseases, repair and regeneration of bone defects have become a research difficulty. Poly (lactic-co-glycolic acid) (PLGA) is a few biomedical materials approved by the U.S. Food and Drug Administration (FDA) and has good processability, biocompatibility and degradability, is enzymatically catabolized into carbon dioxide and water in the human body, and is excreted through urine. However, the problems of poor hydrophilicity, low cell activity and the like exist, and the development of implant tissue engineering is limited.
Piezoelectric ceramic barium titanate (BaTiO) 3 ) The piezoelectric ceramic has good hydrophilicity and biocompatibility, is internally polarized under the action of external force, and has charges on the surface to form an electric field, and the generated piezoelectric signals can promote cell proliferation and differentiation and tissue regeneration, thereby having obvious promotion effect on the generation of new tissues. Thus, the piezoelectric material BaTiO with bioelectrical activity 3 Applied to PLGA biological scaffolds, the generated electric signal turns on Ca 2+ Channels and further activate cell growth pathways. Eventually, cell proliferation, differentiation and expression of gene transcription are promoted. Meanwhile, baTiO 3 Good hydrophilicity promotes the adhesion and growth of cells on the biological scaffold. However, preparation of BaTiO 3 The biggest difficulty with PLGA bioscaffold is that barium titanate is prone to oxygen vacancies in point defects during synthesis. The absence of oxygen vacancies can distort the oxygen octahedron, so that electrons are easy to capture at the oxygen vacancies, domain wall movement is hindered, oxygen vacancies at the interface are gathered and developed inwards, a defect layer caused by oxygen vacancy gathering has a shielding effect on an electric field, polarization of the piezoelectric material is reduced, and piezoelectric performance is finally reduced.
The Graphene Oxide (GO) nano-sheet has good biocompatibility and larger specific surface area, and the edge sites with the surface exposed with a large number of oxygen-related surface functional groups can be used as BaTiO 3 Nucleation sites for direct growth, more importantly, oxygen functionality of GO activates BaTiO 3 Healing of oxygen vacancies in crystals, improving BaTiO 3 Piezoelectric properties of (2). In addition, the GO crystallinity can be improved through chemical reduction in the hydrothermal reaction process, the internal resistance is reduced through forming a conducting path formed by reducing graphene oxide grids, the effective transmission of charges is promoted, and the output voltage signal is improved. Thus, baTiO 3 Hydrothermal synthesis on GO nanoplatelets, then adding PLGA, and preparing degradable BaTiO by using selective laser additive manufacturing (SLS) 3 -GO/PLGA porous scaffold. On one hand, the characteristics of layer-by-layer accumulation and free forming of additive manufacturing are utilized to realize the tailoring of the external contour of the regenerated tissue organ and the accurate control of the internal structure; on the other hand, the aim of gradually degrading the degradable biological stent until finally disappearing while inducing the tissue growth is realized by skillfully utilizing the degradation characteristic of the degradable material.
No BaTiO is currently utilized 3 Is used to regulate cell behavior and tissue remodeling in order to enhance the electrical microenvironment in PLGA bioscaffold.
Disclosure of Invention
To solve the problem that the polymer poly (lactic-co-glycolic acid) (PLGA) biological scaffold directly introduces barium titanate (BaTiO) 3 ) When oxygen vacancies exist to cause BaTiO 3 The invention aims to provide a graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological scaffold and a preparation method thereof. In one aspect, baTiO 3 Hydrothermal synthesis on GO nano-sheet, the edge site of GO surface exposed with oxygen related surface functional group can be used as BaTiO 3 Nucleation sites for direct growth, more importantly, oxygen functionality of GO activates BaTiO 3 Healing of oxygen vacancies in crystals, improving BaTiO 3 Is used for the piezoelectric properties of the piezoelectric element. On the other hand, the GO crystallinity can be improved through chemical reduction in the hydrothermal reaction process, the internal resistance is reduced through forming a conducting path formed by reducing graphene oxide grids, the effective transmission of charges is promoted, and the output voltage signal is improved. In addition to that, baTiO 3 And GO has excellent hydrophilicity, so that the adhesion and growth of cells on the PLGA composite scaffold are improved; baTiO 3 GO also acts as a bridge to enhance the mechanical properties of PLGA scaffolds. The composite biological scaffold has good biocompatibility after being plantedThe biological scaffold can provide living three-dimensional space for cells, is favorable for the cells to obtain enough nutrient substances, performs substance exchange, discharges metabolic products and enables the cells to reproduce and grow on the prefabricated three-dimensional porous scaffold, thereby achieving the aims of repairing and regenerating.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of graphene oxide improved barium titanate/poly (lactic-co-glycolic acid) biological scaffold, comprising the following steps:
step one, baTiO grows on GO nano-sheets through hydrothermal reaction 3 Obtaining BaTiO 3 -GO powder;
dispersing PLGA powder in absolute ethyl alcohol to obtain PLGA suspension, and then adding BaTiO 3 Dispersing GO powder into PLGA suspension to obtain BaTiO 3 The GO/PLGA mixed suspension is subjected to the steps of ultrasonic treatment, magnetic stirring, centrifugation, drying, grinding and the like to obtain BaTiO 3 -GO/PLGA composite powder;
step three, baTiO 3 Production of BaTiO from GO/PLGA composite powder by selective laser additive manufacturing technique 3 -GO/PLGA bioscaffold.
Preferably, in the first step, the synthetic BaTiO is prepared 3 The steps of the solution are as follows: dispersing titanium tetrachloride in ethanol and performing ultrasonic treatment to prepare an ethanol solution of titanium tetrachloride; dissolving barium hydroxide in deionized water and carrying out ultrasonic treatment; dropwise adding an ethanol solution of titanium tetrachloride into an aqueous solution of barium hydroxide, and magnetically stirring to obtain a solution containing Ba and Ti; and dropwise adding sodium hydroxide solution into the solution to enable the pH value of the composite solution to reach alkalinity. And then the prepared BaTiO 3 Adding GO into the solution, and sequentially comprising the following steps: adding GO nano-sheets into the prepared BaTiO 3 In the solution, the mixed solution is stirred by magnetic force, and the mixed solution is subjected to hydrothermal reaction under an autoclave. Finally, repeatedly centrifuging and cleaning the solution with deionized water and ethanol, and drying the centrifuged solution with a vacuum oven to obtain BaTiO 3 -GO powder.
Preferably, in the first step, the selected GO nano-sheets have a sheet diameter of 1-5um and a thickness of 0.8-1.2nm.
Preferably, in the first step, the alkaline pH of the solution is greater than 13.
Preferably, in the first step, the molar ratio of BaTiO3 to GO is 3:1 to 9:1.
Preferably, the dispersion mode adopts ultrasonic and magnetic stirring, the ultrasonic dispersion time is 10-60min, and the temperature is 15-40 ℃; the magnetic stirring and dispersing time is 0.5-6h, the speed is 300-800r/min, and the temperature is 30-60 ℃.
Preferably, the temperature of the vacuum drying oven is 50-80 ℃ and the drying time is 5-24h.
Preferably, the centrifugation time is 10-60min and the centrifugation speed is 1000-5000r/min.
Preferably, the powder time is 3-20min after grinding and drying.
The inventors found that BaTiO has only a tetragonal phase 3 The powder has piezoelectric properties, and if the particle size of the barium titanate powder is too small, it is usually in a cubic phase. In addition, the particle size of the powder is too small, so that agglomeration phenomenon is easy to occur, and the BaTiO is not favored 3 Uniform growth on GO nanoplatelets results in reduced piezoelectric properties, bioactivity, etc. of the composite powder.
Preferably, the synthetic BaTiO3 is tetragonal.
Preferably, the particle size of the synthesized BaTiO3 powder is 10 to 1000nm.
The inventors found that BaTiO growth on GO nanoplatelets 3 Rather than simple physical adsorption, GO and BaTiO 3 Is combined by Ti-O-C chemical bond.
In the second step, it is preferable that the particle size of PLGA is 0.1-5um and the purity is more than 99%.
In the second step, it is preferable that the BaTiO 3 In GO/PLGA bioscaffold, baTiO 3 The weight fraction of GO is 5-30% and the weight fraction of PLGA is 70-95%.
In the third step, baTiO is preferably used 3 -GO/PLGA composite powder is placed in 3DIn the printing system, layer-by-layer sintering is performed according to the set three-dimensional modeling. The preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; and removing the unsintered superfluous powder to obtain the composite biological scaffold.
In the third step, preferably, the process parameters of selective laser sintering are as follows: the laser power is 0.5-4W, the scanning interval is 0.3-1.0mm, the scanning speed is 50-200m/s, the spot diameter is 300-1000mm, and the preheating temperature of the powder bed is 140-160 ℃.
Compared with the prior art, the technical scheme of the invention has the following positive effects:
the invention utilizes GO oxygen functional groups to activate BaTiO 3 Healing of oxygen vacancies in crystals, improving BaTiO 3 To improve the piezoelectric properties of BaTiO 3 The electrical activity of the GO/PLGA biological scaffold constructs an electrical microenvironment for cell growth, and activates a signal path for cell growth, thereby being beneficial to tissue regeneration and reconstruction.
The invention uses BaTiO 3 Adding GO into PLGA matrix to prepare composite biological scaffold, which can utilize BaTiO 3 The GO nano-sheets are used as bridging to improve the mechanical strength of the PLGA stent.
The invention combines BaTiO with good hydrophilicity and biocompatibility 3 And GO is added into the hydrophobic PLGA, so that the hydrophilic property and biocompatibility of the scaffold are improved, and the adhesion, growth, proliferation and differentiation of cells on the scaffold are facilitated.
In the hydrothermal reaction process, GO is partially reduced through chemical reaction, the crystallinity of the GO is improved, the internal resistance is reduced, the effective transmission of charges is promoted, and BaTiO is improved by forming a conducting path formed by reducing graphene oxide grids 3 -output voltage signal of GO/PLGA bioscaffold.
The invention utilizes the selective laser additive manufacturing technology to manufacture the composite biological stent with controllable porosity and personalized customization.
GO and BaTiO in the invention 3 The structure is more stable by Ti-O-C chemical bond combination.
Description of the drawings:
FIG. 1 shows BaTiO according to the invention 3 -preparation flow and characterization diagram of GO/PLGA biological scaffold;
FIG. 2 shows the BaTiO composition of example 1 3 Cell fluorescence patterns after 1,3,5 days of culture on GO/PLGA bioscaffold, demonstrating BaTiO 3 The GO/PLGA biological scaffold is non-biotoxic and suitable for cell growth;
FIG. 3 shows the BaTiO composition of example 1 3 The optical density values of the GO/PLGA bioscaffold and the PLGA bioscaffold in comparative example 1 reflect the proliferation of cells; it can be seen that BaTiO 3 The GO/PLGA bioscaffold has a higher optical density than the cells on the PLGA bioscaffold, indicating that electrical stimulation can promote proliferation of the cells.
FIG. 4 shows BaTiO in example 1 3 Osteogenic differentiation alizarin red staining pattern after 10,13,16 days of culture on GO/PLGA bioscaffold, illustrating BaTiO 3 The GO/PLGA bioscaffold promotes cell differentiation.
The specific embodiment is as follows:
the following describes the invention in more detail with reference to specific examples, but the invention is not limited thereto.
Example 1:
(1) Dispersing 0.1M titanium tetrachloride in 40mL of ethanol, and performing ultrasonic dispersion for 1 hour to fully dissolve to obtain an ethanol solution of titanium tetrachloride; dissolving 0.3M barium hydroxide in 80mL of deionized water, and performing ultrasonic dissolution for 1 hour to fully dissolve to obtain barium hydroxide aqueous solution; dripping ethanol solution containing titanium tetrachloride into aqueous solution containing barium hydroxide, performing ultrasonic treatment for 0.5 hour and magnetic stirring for 1 hour to obtain solution containing Ba and Ti; dropwise adding 0.3mol/L sodium hydroxide solution into the solution containing Ba and Ti to enable the pH value of the composite solution to reach 13; adding the GO nano-sheets into the solution obtained in the previous step, performing ultrasonic treatment for 30 minutes, and magnetically stirring for 2 hours to prevent the GO nano-sheets from aggregation and precipitation; carrying out hydrothermal reaction on the prepared mixed solution under an autoclave at the temperature of 240 ℃ for 48 hours; the solution was repeatedly washed with deionized water and ethanol for 30 minutes at a centrifugation speed of 1000r/min. Finally, drying the centrifuged solution in a vacuum oven at 80 ℃ for 12 hours to obtainBaTiO 3 -GO powder;
(2) Dispersing 19g of PLGA powder in 500mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 1 hour at the ultrasonic temperature of 25 ℃ to obtain PLGA suspension; 1g of BaTiO is then added 3 Dispersing GO powder into PLGA suspension, ultrasonic dispersing for 30 min, magnetic stirring for 4 hr, and magnetic stirring for 25 deg.C to obtain uniformly dispersed BaTiO 3 -GO/PLGA mixed suspension; then centrifugal treatment is carried out, the centrifugal time is 1 hour, the centrifugal rotating speed is 1000r/min, the drying time is 12 hours, the powder time after grinding and drying is 10 minutes, and the BaTiO is obtained 3 -GO/PLGA composite powder.
(3) BaTiO is mixed with 3 The GO/PLGA composite powder is placed in a 3D printing device, and the biological scaffold is prepared by layer-by-layer sintering according to the setting of three-dimensional modeling software. The preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; removal of unsintered excess powder to obtain BaTiO 3 GO/PLGA bioscaffold, designated as 5wt% BaTiO 3 -GO/PLGA; the main technological parameters are as follows: the laser power is 1.0W, the scanning interval is 0.4mm, the scanning speed is 100m/s, the spot diameter is 400mm, and the preheating temperature of the powder bed is 150 ℃.
In this example, baTiO 3 The piezoelectric constant of the GO/PLGA composite biological scaffold is 1.0pC/N; in cell experiments, in BaTiO 3 The GO/PLGA composite biological scaffold cultures cells, the cells have almost no dead cells, the number of the cells is obviously increased along with the increase of time, and the cell has good biocompatibility; cell proliferation using the CCK-8 test, the absorbance increased from 0.2 on the first day to 1.0 on the fifth day.
In this example, baTiO 3 The hydrophilic angle of the GO/PLGA scaffold was 55 °.
In the embodiment, the compressive strength of the biological composite stent is found to be 30MPa by mechanical property test.
In this example, the mass loss after 28 days of immersion in simulated body fluid reaches 10%.
In this example, the tensile test found that BaTiO 3 -GO/PLGA composite biological scaffoldHas a tensile strength of 14MPa, and BaTiO was observed by a scanning electron microscope 3 -GO has bridging in the tensile fracture plane of the composite bioscaffold.
Example 2:
(1) Dispersing 0.5M titanium tetrachloride in 70mL of ethanol, and performing ultrasonic dispersion for 0.5 hour to fully dissolve to obtain an ethanol solution of titanium tetrachloride; dissolving 0.4M barium hydroxide in 120mL of deionized water, and dissolving by ultrasonic for 0.5 hour to obtain barium hydroxide aqueous solution; dripping ethanol solution containing titanium tetrachloride into aqueous solution containing barium hydroxide, performing ultrasonic treatment for 1 hour and magnetic stirring for 2 hours to obtain solution containing Ba and Ti; dropwise adding 0.2mol/L sodium hydroxide solution into the solution containing Ba and Ti to enable the pH value of the composite solution to reach 14; adding the GO nano-sheets into the solution obtained in the previous step, performing ultrasonic treatment for 1 hour, and performing magnetic stirring for 3 hours to prevent the GO nano-sheets from aggregation and precipitation; carrying out hydrothermal reaction on the prepared mixed solution under an autoclave at 220 ℃ for 36 hours; the solution was repeatedly washed with deionized water and ethanol for a centrifugation time of 40 minutes at a centrifugation speed of 1500r/min. Finally, drying the centrifuged solution in a vacuum oven at 70 ℃ for 14 hours to obtain BaTiO 3 -GO powder.
(2) Dispersing 18g of PLGA powder in 400mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 0.5 hour at the ultrasonic temperature of 30 ℃ to obtain PLGA suspension; then 2g of BaTiO 3 Dispersing GO powder into PLGA suspension, ultrasonic dispersing for 40 min, magnetic stirring for 6 hr, and magnetic stirring for 30deg.C to obtain uniformly dispersed BaTiO 3 -GO/PLGA mixed suspension; and then carrying out centrifugal treatment for 0.5 hour at a centrifugal speed of 2000r/min for 9 hours, grinding and drying for 5 minutes to obtain BaTiO 3 -GO/PLGA composite powder.
(3) BaTiO is mixed with 3 The GO/PLGA composite powder is placed in a 3D printing device, and the biological scaffold is prepared by layer-by-layer sintering according to the setting of three-dimensional modeling software. The preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; removal of unsintered excess powder to obtain BaTiO 3 GO/PLGA bioscaffold, recorded as 10wt% BaTiO 3 -GO/PLGA. The main technological parameters are as follows: the laser power is 2.0W, the scanning interval is 0.5mm, the scanning speed is 200m/s, the spot diameter is 500mm, and the preheating temperature of the powder bed is 155 ℃.
In this example, baTiO 3 The piezoelectric constant of the GO/PLGA composite bioscaffold was 0.9pC/N. In cell experiments, in BaTiO 3 The GO/PLGA composite biological scaffold cultures cells, the cells have few dead cells, and the number of the cells is obviously increased along with the increase of time, so that the GO/PLGA composite biological scaffold has good biocompatibility. Cell proliferation using the CCK-8 test, the absorbance increased from 0.18 on the first day to 1.2 on the fifth day.
In this example, baTiO 3 The hydrophilic angle of the GO/PLGA scaffold was 55 °.
In the embodiment, the compressive strength of the biological composite stent is found to be 32MPa by mechanical property test.
In this example, the mass loss after 28 days of immersion in simulated body fluid reaches 14%.
In this example, the tensile test found that BaTiO 3 The tensile strength of the GO/PLGA composite biological scaffold is 15MPa.
Example 3:
(1) Dispersing 0.4M titanium tetrachloride in 60mL of ethanol, and performing ultrasonic dispersion for 40 minutes to fully dissolve to obtain an ethanol solution of titanium tetrachloride; dissolving 0.8M barium hydroxide in 70mL of deionized water, and performing ultrasonic dissolution for 40 minutes to fully dissolve to obtain barium hydroxide aqueous solution; dripping ethanol solution containing titanium tetrachloride into aqueous solution containing barium hydroxide, performing ultrasonic treatment for 1 hour and magnetic stirring for 4 hours to obtain solution containing Ba and Ti; dropwise adding 0.4mol/L sodium hydroxide solution into the solution containing Ba and Ti to enable the pH value of the composite solution to reach 13.5; adding the GO nano-sheets into the solution obtained in the previous step, performing ultrasonic treatment for 40 minutes, and magnetically stirring for 1 hour to prevent the GO nano-sheets from aggregation and precipitation; carrying out hydrothermal reaction on the prepared mixed solution under an autoclave at the temperature of 250 ℃ for 24 hours; the solution was repeatedly washed with deionized water and ethanol for a centrifugation time of 40 minutes at a centrifugation speed of 1200r/min. Finally, the centrifuged solution is dried in vacuum at 70 DEG CDrying in a box for 10 hours to obtain BaTiO 3 -GO powder.
(2) 17g of PLGA powder is dispersed in 500mL of absolute ethyl alcohol, and is subjected to ultrasonic treatment for 1 hour at the ultrasonic temperature of 25 ℃ to obtain PLGA suspension; then 3g of BaTiO 3 Dispersing GO powder into PLGA suspension, ultrasonic dispersing for 20min, magnetic stirring for 3 hr, and magnetic stirring for 30deg.C to obtain uniformly dispersed BaTiO 3 -GO/PLGA mixed suspension; and then carrying out centrifugal treatment for 1.5 hours at a centrifugal speed of 1500r/min for 10 hours, grinding and drying for 6 minutes to obtain BaTiO 3 -GO/PLGA composite powder.
(3) BaTiO is mixed with 3 The GO/PLGA composite powder is placed in a 3D printing device, and the biological scaffold is prepared by sintering layer by layer according to the setting of three-dimensional modeling software; the preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; removal of unsintered excess powder to obtain BaTiO 3 GO/PLGA bioscaffold, noted 15wt% BaTiO 3 -GO/PLGA. The main technological parameters are as follows: the laser power is 1.5W, the scanning interval is 0.6mm, the scanning speed is 200m/s, the spot diameter is 600mm, and the powder bed preheating temperature is 145 ℃.
In this example, baTiO 3 The hydrophilic angle of the GO/PLGA scaffold was 50 °.
In the embodiment, the compressive strength of the biological composite stent is found to be 42MPa by mechanical property test.
In this example, the mass loss after 28 days of immersion in simulated body fluid reaches 16%.
Comparative example 1:
(1) 20g of PLGA powder is placed in a 3D printing device, and sintered layer by layer according to the setting of three-dimensional modeling software to prepare the biological scaffold. The preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; the unsintered excess powder was removed to obtain PLGA bioscaffold, designated as 0wt% BaTiO 3 -GO/PLGA. The main technological parameters are as follows: the laser power is 1.0W, the scanning interval is 0.4mm,the scanning speed is 100m/s, the diameter of a light spot is 400mm, and the preheating temperature of a powder bed is 150 ℃.
In this example, the piezoelectric constant of the PLGA bioscaffold was 1.0pC/N. In the cell experiment, cells are cultured in the PLGA biological scaffold, the cells have almost no dead cells, and the number of the cells is obviously increased along with the increase of time, so that the PLGA biological scaffold has good biocompatibility. Cell proliferation using the CCK-8 test, the absorbance increased from 0.1 on the first day to 0.4 on the fifth day.
In this example, the hydrophilic angle of the PLGA scaffold was 90 °.
In this example, the mechanical property test found that the compression strength of the PLGA bioscaffold was 21MPa.
In this example, the mass loss after 28 days of immersion in simulated body fluid reached 8%.
In this example, the tensile test found that the tensile strength of the PLGA bioscaffold was 11MPa.
Comparative example 2:
(1) Dispersing 0.3M titanium tetrachloride in 70mL of ethanol, and performing ultrasonic dispersion for 0.5 hour to fully dissolve to obtain an ethanol solution of titanium tetrachloride; dissolving 0.4M barium hydroxide in 120mL of deionized water, and dissolving by ultrasonic for 0.5 hour to obtain barium hydroxide aqueous solution; dripping ethanol solution containing titanium tetrachloride into aqueous solution containing barium hydroxide, performing ultrasonic treatment for 1 hour and magnetic stirring for 2 hours to obtain solution containing Ba and Ti; dropwise adding 0.2mol/L sodium hydroxide solution into the solution containing Ba and Ti to enable the pH value of the composite solution to reach 14; adding the GO nano-sheets into the solution obtained in the previous step, performing ultrasonic treatment for 1 hour, and performing magnetic stirring for 3 hours to prevent the GO nano-sheets from aggregation and precipitation; carrying out hydrothermal reaction on the prepared mixed solution under an autoclave at 220 ℃ for 36 hours; the solution was repeatedly washed with deionized water and ethanol for a centrifugation time of 40 minutes at a centrifugation speed of 1500r/min. Finally, drying the centrifuged solution in a vacuum oven at 70 ℃ for 14 hours to obtain BaTiO 3 -GO powder.
(2) Dispersing 18.5g of PLGA powder in 400mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 0.5 hour at the ultrasonic temperature of 30 ℃ to obtain PLGA suspension; 1.5g of BaTiO is then added 3 Dispersing GO powder into PLGA suspension, ultrasonic dispersing for 40 min, magnetic stirring for 6 hr, and magnetic stirring for 30deg.C to obtain uniformly dispersed BaTiO 3 -GO/PLGA mixed suspension; and then carrying out centrifugal treatment for 0.5 hour at a centrifugal speed of 2000r/min for 9 hours, grinding and drying for 5 minutes to obtain BaTiO 3 -GO/PLGA composite powder.
(3) BaTiO is mixed with 3 The GO/PLGA composite powder is placed in a 3D printing device, and the biological scaffold is prepared by layer-by-layer sintering according to the setting of three-dimensional modeling software. The preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; removal of unsintered excess powder to obtain BaTiO 3 GO/PLGA bioscaffold, noted as 7.5wt% BaTiO 3 -GO/PLGA. The main technological parameters are as follows: the laser power is 2.0W, the scanning interval is 0.5mm, the scanning speed is 200m/s, the spot diameter is 500mm, and the preheating temperature of the powder bed is 155 ℃.
In this example, baTiO 3 The piezoelectric constant of the GO/PLGA composite bioscaffold was 0.8pC/N. In cell experiments, in BaTiO 3 The GO/PLGA composite biological scaffold cultures cells, the cells have almost no dead cells, and the number of the cells is obviously increased along with the increase of time, so that the GO/PLGA composite biological scaffold has good biocompatibility. Cell proliferation using the CCK-8 test, the absorbance increased from 0.18 on the first day to 1.1 on the fifth day.
In this example, the hydrophilic angle of the BaTiO3-GO/PLGA scaffold was 53.
In the embodiment, the compressive strength of the biological composite stent is found to be 30.2MPa by mechanical property test.
In this example, the mass loss after 28 days of immersion in simulated body fluid reaches 12%.
In this example, tensile experiments found that the tensile strength of the BaTiO3-GO/PLGA composite bioscaffold was 12.4MPa.
Comparative example 3
(1) Dispersing 0.1M titanium tetrachloride in 60mL of ethanol, and performing ultrasonic dispersion for 40 minutes to fully dissolve to obtain ethanol solution of titanium tetrachlorideA liquid; dissolving 0.3M barium hydroxide in 70mL of deionized water, and performing ultrasonic dissolution for 40 minutes to fully dissolve to obtain barium hydroxide aqueous solution; dripping ethanol solution containing titanium tetrachloride into aqueous solution containing barium hydroxide, performing ultrasonic treatment for 1 hour and magnetic stirring for 4 hours to obtain solution containing Ba and Ti; dropwise adding 0.4mol/L sodium hydroxide solution into the solution containing Ba and Ti to enable the pH value of the composite solution to reach 13.5; adding the GO nano-sheets into the solution obtained in the previous step, performing ultrasonic treatment for 40 minutes, and magnetically stirring for 1 hour to prevent the GO nano-sheets from aggregation and precipitation; carrying out hydrothermal reaction on the prepared mixed solution under an autoclave at the temperature of 250 ℃ for 24 hours; the solution was repeatedly washed with deionized water and ethanol for a centrifugation time of 40 minutes at a centrifugation speed of 1200r/min. Finally, drying the centrifuged solution in a vacuum oven at 70 ℃ for 10 hours to obtain BaTiO 3 -GO powder.
(2) 15g of PLGA powder is dispersed in 500mL of absolute ethyl alcohol, and is subjected to ultrasonic treatment for 1 hour at the ultrasonic temperature of 25 ℃ to obtain PLGA suspension; then 5g of BaTiO 3 Dispersing GO powder into PLGA suspension, ultrasonic dispersing for 20min, magnetic stirring for 3 hr, and magnetic stirring for 30deg.C to obtain uniformly dispersed BaTiO 3 -GO/PLGA mixed suspension; and then carrying out centrifugal treatment for 1.5 hours at a centrifugal speed of 1500r/min for 10 hours, grinding and drying for 6 minutes to obtain BaTiO 3 -GO/PLGA composite powder.
(3) BaTiO is mixed with 3 The GO/PLGA composite powder is placed in a 3D printing device, and the biological scaffold is prepared by layer-by-layer sintering according to the setting of three-dimensional modeling software. The preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; removal of unsintered excess powder to obtain BaTiO 3 GO/PLGA bioscaffold, noted 25wt% BaTiO 3 -GO/PLGA. The main technological parameters are as follows: the laser power is 1.5W, the scanning interval is 0.6mm, the scanning speed is 200m/s, the spot diameter is 600mm, and the powder bed preheating temperature is 145 ℃.
In this example, the hydrophilic angle of the BaTiO3-GO/PLGA scaffold was 44 °.
In this example, the mechanical property test found that the compressive strength of the biocomposite stent was 50MPa.
In this example, the mass loss after 28 days of immersion in simulated body fluid reaches 15%.
Claims (5)
1. The preparation method of the graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological scaffold is characterized by comprising the following steps of:
step one, firstly preparing and synthesizing BaTiO 3 The steps of the solution are as follows: dispersing titanium tetrachloride in ethanol and performing ultrasonic treatment to prepare an ethanol solution of titanium tetrachloride; dissolving barium hydroxide in deionized water and carrying out ultrasonic treatment; dropwise adding an ethanol solution of titanium tetrachloride into an aqueous solution of barium hydroxide, and magnetically stirring to obtain a solution containing Ba and Ti; dropwise adding a sodium hydroxide solution into the solution to enable the pH value of the composite solution to reach alkalinity; and then the prepared BaTiO 3 Adding GO into the solution, and sequentially comprising the following steps: adding GO nano-sheets into the prepared BaTiO 3 In the solution, after ultrasonic dispersion, magnetically stirring, and carrying out hydrothermal reaction on the mixed solution under an autoclave; finally, repeatedly centrifuging and cleaning the solution with deionized water and ethanol, and drying the centrifuged solution with a vacuum oven to obtain BaTiO3-GO powder;
dispersing PLGA powder in absolute ethyl alcohol to obtain PLGA suspension, and then adding BaTiO 3 Dispersing GO powder into PLGA suspension to obtain BaTiO 3 The GO/PLGA mixed suspension is subjected to the steps of ultrasonic, magnetic stirring, centrifugation, drying and grinding to obtain BaTiO 3 -GO/PLGA composite powder;
step three, baTiO 3 Placing the GO/PLGA composite powder in a 3D printing system, and sintering layer by layer according to the set three-dimensional modeling; the preparation method of the biological scaffold comprises the following steps of: preheating the powder to a temperature slightly below the melting point; flattening the rod-spread powder; sintering the powder layer by a laser beam; removing unsintered superfluous powder to obtain a composite biological scaffold;
in the first step, GO nano-sheets are dispersed in BaTiO 3 The ultrasonic dispersion time in the solution is 10-60min, the temperature is 15-40 ℃; the magnetic stirring and dispersing time is 0.5-6h, the speed is 300-800r/min, and the temperature is 30-60 ℃; the centrifugation time is 10-60min, and the centrifugation speed is 1000-5000r/min; the temperature of the vacuum drying oven is 50-80 ℃ and the drying time is 5-24h; grinding and drying for 3-20min;
in the second step, the particle size of PLGA is 0.1-5um, and the purity is more than 99%; the BaTiO 3 In the-GO/PLGA composite powder, baTiO 3 -GO 5-30% by weight and PLGA 70-95% by weight;
in the third step, the technological parameters of selective laser sintering are as follows: the laser power is 0.5-4W, the scanning interval is 0.3-1.0mm, the scanning speed is 50-200m/s, the spot diameter is 300-1000mm, and the preheating temperature of the powder bed is 140-160 ℃.
2. The method for preparing the graphene oxide improved barium titanate/poly (lactic-co-glycolic acid) biological scaffold according to claim 1, wherein in the first step, the selected GO nano-sheets have a sheet diameter of 1-5um and a thickness of 0.8-1.2nm.
3. The method for preparing a graphene oxide-modified barium titanate/poly (lactic-co-glycolic acid) bioscaffold according to claim 1, wherein in the first step, the PH of the composite solution is greater than 13.
4. The method for preparing a graphene oxide-modified barium titanate/poly (lactic-co-glycolic acid) bioscaffold according to claim 1, wherein in the first step, baTiO 3 The molar ratio of the catalyst to GO is 3:1-9:1.
5. The method for preparing a graphene oxide-modified barium titanate/poly (lactic-co-glycolic acid) bioscaffold according to claim 1, wherein in the first step, the synthesized BaTiO is 3 Is tetragonal phase, synthesized BaTiO 3 The particle size of the powder is 10-1000nm.
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