CN104592725A - Polylactic acid composite material for promoting bone growth and biocompatibility and preparation method of polylactic acid composite material - Google Patents
Polylactic acid composite material for promoting bone growth and biocompatibility and preparation method of polylactic acid composite material Download PDFInfo
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- CN104592725A CN104592725A CN201410838299.8A CN201410838299A CN104592725A CN 104592725 A CN104592725 A CN 104592725A CN 201410838299 A CN201410838299 A CN 201410838299A CN 104592725 A CN104592725 A CN 104592725A
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Abstract
The invention relates to a polylactic acid composite material for promoting bone growth and biocompatibility and a preparation method of the polylactic acid composite material. The preparation method comprises the following steps: by adopting polylactic acid and pearl powder as raw materials, dissolving by a solvent, and carrying out magnetic stirring, ultrasonic dispersion, solvent evaporation and solvent desorption to obtain the pearl-powder-containing modified polylactic acid composite material. The material is soaked in a simulated body fluid (SBF); by adopting a biomimetic mineralization technology, hydroxyapatite (HA) grows on the material. Result shows that the material product has favorable stability and uniformity; due to the presence of the pearl powder, the growth velocity of the HA is remarkably improved; along with the content addition of the pearl powder, the mineralization speed of the HA is continuously improved. A test through an MTT method proves that the biocompatibility and the cell relative growth rate of the material is improved to a large extent on the basis of pure polylactic acid due to the presence of the pearl powder; and the enhancing effect of the composite material with high pearl powder content is more considerable. The composite material shows bright prospect as a bone repair material.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of lactic acid composite material and the preparation method that promote osteogenesis and biocompatibility, particularly relate to and a kind ofly adopt having of pearl powder and poly(lactic acid) compound to induce hydroxyapatite to grow and biocompatibility improves double effects lactic acid composite material and preparation method thereof, specifically, be that the having of pearl powder be dispersed with in a kind of poly(lactic acid) through polyoxyethylene glycol surface modification induces hydroxyapatite growth and biocompatibility to improve double effects lactic acid composite material and preparation method thereof.
Background technology
Along with the development of Materials science, increasing material enters the defect of medical field as bio-medical material reparation partes corporis humani position, and bone renovating material is exactly one of them.Current various artificial implantation emerges in an endless stream, wherein mainly contain the kinds such as metal bone support (as Ti etc.), biological ceramics (as HA, TCP etc.) and macromolecular material (as PLA, PGA, PCL etc.), but mainly play the effect of bone support mechanical support, not there is bone-inducting active specific to bone growth factor.Kun recklessly, Zhang Yu, mention in " progress of hydroxyapatite/polylactic acid artificial bone repair materials " of the people such as Ren Weiwei on " Chinese Orthopedic Clinical and fundamental research magazine; 2013; 5 (1): 56-62 ", desirable bone renovating material should possess good biocompatibility, mechanical property, biological degradability and regeneration induction, wherein, and the biomaterial that poly(lactic acid) is comparatively given prominence to as an over-all properties and gaining great popularity.But taking poly(lactic acid) as the bone renovating material of main component, there will be physical strength not, the shortcoming such as comparatively slow, the aseptic inflammation reaction of degradation rate and cytotoxicity, therefore carried out considerable modification work at the bone-repairing composite material taking poly(lactic acid) as matrix.Hydroxyapatite is as the chief component of human bone, obtain suitable concern and as main material modified, but James M.Anderson and Kathleen M.Miller is report in " Biomaterials; 1984; 5 (1): 5-10 ", also there will be slighter inflammatory reaction in the bone renovating material taking HA as main component.Coupling agent can be used for the degradation rate improving PLA, therefore PLA/HA matrix material is prepared with after coupling agent pre-treatment HA in " Materials science & engineering C; Materials for biological applications; 2012; 32 (6): 1428-36 ", but show lower cell compatibility, this owing to the poisonous small molecules of acidity produced after PLA degraded, local will be unfavorable for growth and the adhesion of cell.In addition, the stability that HA is very high is not enough to the slant acidity environment that alleviation PLA causes.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, a kind of lactic acid composite material and the preparation method that promote osteogenesis and biocompatibility are provided, namely one have induction hydroxyapatite growth and biocompatibility improve double effects lactic acid composite material and preparation method thereof, particularly providing a kind of adopts having of pearl powder and poly(lactic acid) compound to induce hydroxyapatite to grow and biocompatibility improves double effects lactic acid composite material and preparation method thereof, specifically, that the having of pearl powder be dispersed with in a kind of poly(lactic acid) through polyoxyethylene glycol surface modification induces hydroxyapatite growth and biocompatibility to improve double effects lactic acid composite material and preparation method thereof.The present invention is using the intermingling material of poly(lactic acid) and pearl powder as matrix, it has can induce hydroxyapatite to grow and impel effect of cell proliferation, that is, the mixture of pearl powder and poly(lactic acid) can grow more hydroxyapatite (in simulated body fluid empirical tests) than pure poly(lactic acid), and its increment along with pearl powder content and soak time increase and increase, in addition, pearl powder detects with the cytotoxicity of polylactic acid composition and proves that this matrix material has better cell compatibility than simple poly-lactic acid material, and cell proliferation rate is greatly improved.Matrix material of the present invention adopts and be mixed into pearl powder in PLA solution simultaneously, and obtain film like matrix material by cast molding, method is simply efficient, cost is lower, before adding pearl powder, first surface activation process is carried out to pearl powder, make it in use can be dispersed in very uniformly in whole compound system, after ultrasonic, dispersion effect is better.
A kind of lactic acid composite material promoting osteogenesis and biocompatibility of the present invention, described lactic acid composite material is the compound system of poly(lactic acid) and pearl powder, pearl powder in the inside of poly(lactic acid) and surface uniform dispersion, and is exposed to surface and fully contacts with external environment.
As preferred technical scheme:
Described a kind of lactic acid composite material promoting osteogenesis and biocompatibility as above, the total amount of pearl powder is 1 ~ 50wt% of described lactic acid composite material.
Described a kind of lactic acid composite material promoting osteogenesis and biocompatibility as above, described pearl powder is the pearl powder through polyoxyethylene glycol surface modification.
Described a kind of lactic acid composite material promoting osteogenesis and biocompatibility as above, described lactic acid composite material is film, and thickness is 80 ~ 200 μm.
Present invention also offers a kind of preparation method promoting the lactic acid composite material of osteogenesis and biocompatibility, comprise the following steps:
(1) the surface activation process of pearl powder;
Pearl powder is joined in deionized water, adds polyoxyethylene glycol powder simultaneously, stir and ultrasonic after, freezing at-15 ~-20 DEG C, then lyophilize, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
Poly(lactic acid) is dissolved and is configured to solution in a solvent, then will add in solution through poly ethyldiol modified pearl powder, through stirring and after supersound process, being cast to after in sheet glass or watch-glass, remove solvent;
Poly(lactic acid)/pearl powder mixture is immersed in NaOH solution with Partial digestion poly(lactic acid) surface, make pearl powder be exposed to material surface and contact external environment, clean and dry, obtain the lactic acid composite material that wetting ability is improved greatly, for mineralisation process and Growth of Cells provide desirable environment.
Preparation method as above, the particle size of pearl powder is 100 ~ 400nm; The polymerization degree of polyoxyethylene glycol is 4000 ~ 10000Da; Polyoxyethylene glycol and pearl powder mass ratio are 2:98 ~ 5:95, the two quality and with deionized water quality than for 1:10 ~ 1:20; Described stirring also ultrasonicly refers to that stir speed (S.S.) is 500 ~ 1000rpm, ultrasonic power 40 ~ 50KHz, and the time is respectively 0.5 ~ 1h, obtains the homodisperse solution of pearl powder; The described freezing time is 12 ~ 15h; Described lyophilize is at-55 ~-45 DEG C, used time 20 ~ 24h.
Preparation method as above, poly(lactic acid) weight-average molecular weight is 70000 ~ 200000; Described solvent is the good solvent such as trichloromethane or Isosorbide-5-Nitrae dioxane; Poly(lactic acid) is dissolved and is configured to the solution that massfraction is 5-10wt% in a solvent; To add in solution through poly ethyldiol modified pearl powder, pearl powder concentration is 1 ~ 50wt%; Described stirring and supersound process refer to that stir speed (S.S.) is 800 ~ 1000rpm and ultrasonic power 40 ~ 50KHz, and the time is respectively 0.5 ~ 1h;
Preparation method as above, then described removal solvent puts into 50 ~ 60 DEG C of vacuum drying oven 10-12h, to remove residual solvent after referring to and place 10 ~ 12h under room temperature environment.
Preparation method as above, the mass concentration of NaOH solution is 1 ~ 2M, and soak time is 10 ~ 20min.
Modern pharmacological research display pearl powder contains the protein of 5%, comprises 18 seed amino acids such as leucine, methionine(Met), L-Ala, 20 various trace elements and vitamins B, the calcium carbonate of 95% aragonite structure.Its effect comprises enhancing body immunologic function, and beauty treatment, the cell regeneration of promotion skin collagen, strengthen skin elasticity.Pearl powder also has more significant antiinflammation, can inflammation-inhibiting cell regeneration, prevents wound from worsening further.The present invention is using the intermingling material of poly(lactic acid) and pearl powder as matrix, and have the growth of induction hydroxyapatite and impel the performance of cell proliferation, have better cell compatibility, cell proliferation rate is greatly improved simultaneously.
Beneficial effect
(1) in selected in the present invention material system, pearl powder and poly(lactic acid) are commercially produced product, and manufacturer is numerous, and large-scale industrial production widely, therefore can be carried out in source.
(2) for the pre-treatment of pearl powder, there is certain scientific basis in the present invention, utilize tensio-active agent to be dispersed in organism poly(lactic acid) by inorganics pearl powder, and selected table surface-active agent has good biocompatibility too to human body.
(3) pearl powder is employed in prepared in the present invention material, it has good promoter action in hydroxyapatite process of growth, instead of other bone growth factors, greatly reduce Bone Defect Repari cost, economic benefit has very considerable prospect.
(4) in prepared in the present invention material, while poly(lactic acid) degraded, the surface of pearl powder can be exposed, the pearl powder being wrapped in internal layer is not discharged and can not be degraded, so successfully serve the effect of pearl powder slowly-releasing, continually in Bone Defect Repari process can provide pearl powder, reach best Bone Defect Repari effect.
(5) prepared in the present invention material, while improve biocompatibility, also accelerates the speed of HA biomimetic mineralization, in Bone Defect Repari field, has great application prospect.
Accompanying drawing explanation
Fig. 1 a, 1b, 1c are the pure poly(lactic acid) of non-biomimetic mineralization and the shape appearance figure of poly(lactic acid)/pearl powder laminated film: Fig. 1 a is pure poly(lactic acid) surface; Fig. 1 b is 10wt% pearl powder/poly(lactic acid) surface; Fig. 1 c is 10wt% pearl powder/poly(lactic acid) cross section
Fig. 2 a, 2b, 2c are that poly(lactic acid)/pearl powder laminated film soaks the surface topography map after 1 day in 1.5 times of simulated body fluids: Fig. 2 a is pure poly(lactic acid) surface; Fig. 2 b is 10wt% pearl powder/poly(lactic acid) surface; Fig. 2 c is 20wt% pearl powder/poly(lactic acid) surface
Fig. 3 a, 3b, 3c are that poly(lactic acid)/pearl powder laminated film soaks the surface topography map after 3 days in 1.5 times of simulated body fluids: Fig. 3 a is pure poly(lactic acid) surface; Fig. 3 b is 10wt% pearl powder/poly(lactic acid) surface; Fig. 3 c is 20wt% pearl powder/poly(lactic acid) surface
Fig. 4 is the material weightening finish and pearl powder content and the graphic representation soaking number of days that obtain after poly(lactic acid)/pearl powder laminated film soaks in 1.5 times of simulated body fluids
Embodiment
A kind of lactic acid composite material promoting osteogenesis and biocompatibility of the present invention, described lactic acid composite material is the compound system of poly(lactic acid) and pearl powder, pearl powder in the inside of poly(lactic acid) and surface uniform dispersion, and is exposed to surface and fully contacts with external environment.
Wherein, the total amount of pearl powder is 1 ~ 50wt% of described lactic acid composite material; Pearl powder is the pearl powder through polyoxyethylene glycol surface modification; Lactic acid composite material is film, and thickness is 80 ~ 200 μm.
Fig. 4 is the graphic representation of material weightening finish and pearl powder content and the soak time obtained after poly(lactic acid)/pearl powder laminated film soaks in 1.5 times of simulated body fluids.As can be seen from Figure 4, for the poly-lactic acid material not adding pearl powder, its weightening finish rule is the prolongation first exponentially type growth along with soak time, increases subsequently according to certain rate stabilization.And with the addition of the poly-lactic acid material of pearl powder, its initial rate of gain is increased dramatically, and increase along with the increase of pearl powder addition, and almost reach the highest initial rate when adding 15wt% to, subsequently also according to same speed steady-state growth, 20wt% is still improved the effect of hydroxyapatite growth velocity in the later stage compared to 15wt%.
In accompanying drawing, Fig. 1 a is the surface topography map of the pure polylactic acid film of non-biomimetic mineralization; Fig. 2 a is that pure polylactic acid film soaks the surface topography map after 1 day in 1.5 times of simulated body fluids; Fig. 3 a is that pure polylactic acid film soaks the surface topography map after 3 days in 1.5 times of simulated body fluids.
Embodiment 1
Promote a preparation method for the lactic acid composite material of osteogenesis and biocompatibility, comprising:
(1) the surface activation process of pearl powder
Be that the pearl powder of 100nm joins in deionized water by particle size, add the polyoxyethylene glycol powder that the polymerization degree is 4000Da, polyoxyethylene glycol and pearl powder mass ratio are 2:98 simultaneously, the two quality and with deionized water quality than for 1:10, stir and ultrasonic after, freezing 12h at-15 DEG C, wherein, stir speed (S.S.) is 1000rpm, ultrasonic power 50KHz, time is respectively 0.5h, and then lyophilize 20h at-55 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
By weight-average molecular weight be 70000 poly(lactic acid) be dissolved in trichloromethane solvent and be configured to the solution that massfraction is 5wt%, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is 1wt%, stir after the ultrasonic 0.5h process of 0.5h and ultrasonic power 40KHz through stir speed (S.S.) 8000rpm, be cast to after in sheet glass, after placing 10h under room temperature environment, then put into 50 DEG C of vacuum drying oven 10h, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 1M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 80 μm.
Embodiment 2
Promote a preparation method for the lactic acid composite material of osteogenesis and biocompatibility, comprising:
(1) the surface activation process of pearl powder
Be that the pearl powder of 400nm joins in deionized water by particle size, add the polyoxyethylene glycol powder that the polymerization degree is 10000Da, polyoxyethylene glycol and pearl powder mass ratio are 5:95 simultaneously, the two quality and with deionized water quality than for 1:20, stir and ultrasonic after, freezing 15h at-20 DEG C, wherein, stir speed (S.S.) is 500rpm, ultrasonic power 40KHz, time is respectively 1h, and then lyophilize 24h at-45 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
By weight-average molecular weight be 200000 poly(lactic acid) be dissolved in 1, the solution that massfraction is 10wt% is configured in 4 dioxane solvent, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is 50wt%, stir after the ultrasonic 1h process of 1h and ultrasonic power 50KHz through stir speed (S.S.) 1000rpm, be cast to after in watch-glass, after placing 12h under room temperature environment, then 60 DEG C of vacuum drying oven 12h are put into, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 2M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 200 μm.
Embodiment 3
Promote a preparation method for the lactic acid composite material of osteogenesis and biocompatibility, comprising:
(1) the surface activation process of pearl powder
Be that the pearl powder of 300nm joins in deionized water by particle size, add the polyoxyethylene glycol powder that the polymerization degree is 5000Da, polyoxyethylene glycol and pearl powder mass ratio are 2:98 simultaneously, the two quality and with deionized water quality than for 1:18, stir and ultrasonic after, freezing 12h at-16 DEG C, wherein, stir speed (S.S.) is 600rpm, ultrasonic power 45KHz, time is respectively 0.6h, and then lyophilize 22h at-50 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
By weight-average molecular weight be 150000 poly(lactic acid) be dissolved in 1, the solution that massfraction is 8wt% is configured in 4 dioxane solvent, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is 10wt%, after stir speed (S.S.) is 900rpm stirring 0.6 and ultrasonic power 45KHz ultrasonic 0.6 processes, be cast to after in sheet glass, after placing 11h under room temperature environment, then 55 DEG C of vacuum drying oven 11h are put into, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 1M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 120 μm.
Embodiment 4
Promote a preparation method for the lactic acid composite material of osteogenesis and biocompatibility, comprising:
(1) the surface activation process of pearl powder
Be that the pearl powder of 100nm joins in deionized water by particle size, add the polyoxyethylene glycol powder that the polymerization degree is 10000Da, polyoxyethylene glycol and pearl powder mass ratio are 3:98 simultaneously, the two quality and with deionized water quality than for 1:11, stir and ultrasonic after, freezing 13h at-15 DEG C, wherein, stir speed (S.S.) is 800rpm, ultrasonic power 40KHz, time is respectively 1h, and then lyophilize 22h at-45 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
By weight-average molecular weight be 100000 poly(lactic acid) be dissolved in trichloromethane solvent and be configured to the solution that massfraction is 8wt%, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is 30wt%, stir after the ultrasonic 1h process of 0.6h and ultrasonic power 48KHz through stir speed (S.S.) 900rpm, be cast to after in sheet glass, after placing 12h under room temperature environment, then put into 50 DEG C of vacuum drying oven 11h, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 1.5M, 15min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 110 μm.
Embodiment 5
Promote a preparation method for the lactic acid composite material of osteogenesis and biocompatibility, comprising:
(1) the surface activation process of pearl powder
Be that the pearl powder of 400nm joins in deionized water by particle size, add the polyoxyethylene glycol powder that the polymerization degree is 4000Da, polyoxyethylene glycol and pearl powder mass ratio are 4:95 simultaneously, the two quality and with deionized water quality than for 1:15, stir and ultrasonic after, freezing 12h at-15 DEG C, wherein, stir speed (S.S.) is 700rpm, ultrasonic power 48KHz, time is respectively 0.8h, and then lyophilize 23h at-55 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
By weight-average molecular weight be 100000 poly(lactic acid) be dissolved in 1, the solution that massfraction is 10wt% is configured in 4 dioxane solvent, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is 1wt%, be, after 800rpm stirs 0.8h and ultrasonic power 48KHz ultrasonic 0.6h process, be cast to after in sheet glass, after placing 10h under room temperature environment through stir speed (S.S.), then 55 DEG C of vacuum drying oven 10h are put into, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 2M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 90 μm.
Embodiment 6
Promote a preparation method for the lactic acid composite material of osteogenesis and biocompatibility, comprising:
(1) the surface activation process of pearl powder
Be that the pearl powder of 400nm joins in deionized water by particle size, add the polyoxyethylene glycol powder that the polymerization degree is 10000Da, polyoxyethylene glycol and pearl powder mass ratio are 5:95 simultaneously, the two quality and with deionized water quality than for 1:20, stir and ultrasonic after, freezing 15h at-20 DEG C, wherein, stir speed (S.S.) is 1000rpm, ultrasonic power 50KHz, time is respectively 1h, and then lyophilize 24h at-45 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
By weight-average molecular weight be 200000 poly(lactic acid) be dissolved in 1, the solution that massfraction is 10wt% is configured in 4 dioxane solvent, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is 50wt%, stir after the ultrasonic 1h process of 1h and ultrasonic power 50KHz through stir speed (S.S.) 1000rpm, be cast to after in watch-glass, after placing 12h under room temperature environment, then 60 DEG C of vacuum drying oven 12h are put into, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 1.5M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 200 μm.
Embodiment 7
(1) preparation of pure poly(lactic acid)
Take weight-average molecular weight be 200000 poly(lactic acid) 2g be dissolved in 1, be configured to the solution that massfraction is 10wt% in 4 dioxane solvent, be cast in watch-glass, after placing 12h under room temperature environment, then 60 DEG C of vacuum drying oven 12h are put into, to remove residual solvent;
Pure poly(lactic acid) being immersed in mass concentration is that in the NaOH solution of 2M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the polylactic acid film that thickness is about 110 μm.
(2) biomimetic mineralization of material surface
Be placed in 1.5 times of simulated body fluids by the pure polylactic acid film of preparation and soak, and cultivate to grow hydroxyapatite at 37 DEG C, take out after 1 day and 3 days, observe its modification of surface morphology, between soak period, every day changes a simulated body fluid.Be the surperficial surface sweeping electron microscopic picture of immersion after 1 day as shown in Figure 2 a, the change that (as shown in Figure 1a) its surface is too not large before non-mineralising, only has fragmentary hydroxyapatite nucleus.Be the surface scan electron microscopic picture of immersion after 3 days as shown in Figure 3 a, compared to immersion 1 day, its surface defined the profile of hydroxylapatite mineralized layer gradually, and increment also increases greatly.
Embodiment 8
(1) the surface activation process of pearl powder
Take pearl powder 0.1g that particle size is 400nm and joined in 5ml deionized water, add the polyoxyethylene glycol powder 1mg that the polymerization degree is 4000Da simultaneously, stir and ultrasonic after, freezing 12h at-20 DEG C, wherein, stir speed (S.S.) is 500rpm, ultrasonic power 40KHz, time is respectively 1h, and then lyophilize 24h at-45 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material
Take weight-average molecular weight be 200000 poly(lactic acid) 1.9g be dissolved in 1, the solution that massfraction is 10wt% is configured in 4 dioxane solvent, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is the 10wt% of solute total amount, stir after the ultrasonic 1h process of 1h and ultrasonic power 50KHz through stir speed (S.S.) 1000rpm, be cast in watch-glass, after placing 12h under room temperature environment, then 60 DEG C of vacuum drying oven 12h are put into, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 2M, 10min is with Partial digestion poly(lactic acid) surface, and clean and dry, obtain the lactic acid composite material that thickness is about 130 μm, Fig. 1 b is seen on surface, and cross section as illustrated in figure 1 c.(3) biomimetic mineralization of composite material surface
Be placed on by described lactic acid composite material in 1.5 times of simulated body fluids and soak, and cultivate to grow hydroxyapatite at 37 DEG C, take out after 1 day and 3 days, observe its modification of surface morphology, between soak period, every day changes a simulated body fluid.Be the surface scan electron microscopic picture of immersion after 1 day as shown in Figure 2 b, before non-mineralising, (as shown in Figure 1 b) its surface generates hydroxyapatite in a large number, but mineralized layer is perfect not.As shown in Figure 3 b for the surperficial surface sweeping electron microscopic picture of immersion after 3 days, compared to immersion 1 day, it is perfect that the mineralized layer on its surface obtains big area, but still can not covering material surface completely, forms surperficial regular hydroxylapatite mineralized layer.Generally speaking, after adding pearl powder, the mineralization rate of material is improved largely.
Embodiment 9
(1) the surface activation process of pearl powder
Take pearl powder 0.2g that particle size is 400nm and joined in 10ml deionized water, add the polyoxyethylene glycol powder 2mg that the polymerization degree is 4000Da simultaneously, stir and ultrasonic after, freezing 12h at-20 DEG C, wherein, stir speed (S.S.) is 500rpm, ultrasonic power 40KHz, time is respectively 1h, and then lyophilize 24h at-45 DEG C, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material
Take weight-average molecular weight be 200000 poly(lactic acid) 1.8g be dissolved in 1, the solution that massfraction is 10wt% is configured in 4 dioxane solvent, to add in solution through poly ethyldiol modified pearl powder again, pearl powder concentration is the 20wt% of solute total amount, stir after the ultrasonic 1h process of 1h and ultrasonic power 50KHz through stir speed (S.S.) 1000rpm, be cast in watch-glass, after placing 12h under room temperature environment, then 60 DEG C of vacuum drying oven 12h are put into, to remove residual solvent;
Poly(lactic acid)/pearl powder mixture being immersed in mass concentration is that in the NaOH solution of 2M, 10min, with Partial digestion poly(lactic acid) surface, cleans and dries, obtain the lactic acid composite material that thickness is 150 μm.
(3) biomimetic mineralization of composite material surface
Be placed on by described lactic acid composite material in 1.5 times of simulated body fluids and soak, and cultivate to grow hydroxyapatite at 37 DEG C, take out after 1 day and 3 days, observe its modification of surface morphology, between soak period, every day changes a simulated body fluid.Be the surface scan electron microscopic picture of immersion after 1 day as shown in Figure 2 c, can find out, in mineralising after 1 day, material surface has defined very complete hydroxylapatite mineralized layer, contacts with each other and be arranged with sequence between spherulite.As shown in Figure 3 c for the surface scan electron microscopic picture of immersion after 3 days, compared to the material surface of mineralising after 1 day, soaking the surperficial mineralized layer after 3 days improves further, and the space between spherulite is filled, surperficial regular and fine and close.Generally speaking, when pearl powder addition reaches 20wt%, its mineralising growth hydroxyapatite in simulated body fluid has reached ideal state.
Embodiment 10
The pure poly(lactic acid) after for some time will be soaked and 20wt% pearl powder/poly-lactic acid material is placed in atmosphere respectively in simulated body fluid, investigate the binding ability of mineralized layer and body material.The mineralized layer on pure poly-lactic acid material surface occurs to depart from curling phenomenon with matrix over time, 20wt% pearl powder/lactic acid composite material then without any change, the matrix material prepared by explanation and between mineralized layer, there is good binding ability.
Embodiment 11
According to above method obtain pearl powder content be respectively 0,5,10,15, the poly(lactic acid)/pearl powder matrix material of 20wt%, use mtt assay to carry out Cytotoxic test.In the present embodiment, MC3T3 cell (mice embryonic scleroblast) was inoculated into material surface after 1,4,7 days, light absorption value under microplate reader records 492nm and 570nm wavelength, with pure poly(lactic acid) for negative control group, its relative proliferation rate is made to be 100%, obtain the relative appreciation rate of the material modified cell relative to pure poly(lactic acid) of each pearl powder content after conversion, its result is as shown in [table 1-2].From result display, along with the raising of pearl powder content, the relative proliferation rate of cell also raises gradually, illustrates that pearl powder has better biological activity, is more conducive to the growth of MC3T3 cell.
The pearl powder modified polylactic acid composite material prepared by the present invention can effectively be induced the growth of hydroxyapatite and improve biocompatibility, and therefore infers the candidate scheme that this method can be prepared as bone renovating material.
The table 1 pearl powder modified polylactic acid composite material surface relative proliferation rate of MC3T3 (492nm)
The table 2 pearl powder modified polylactic acid composite material surface relative proliferation rate of MC3T3 (570nm)
Claims (9)
1. one kind promotes the lactic acid composite material of osteogenesis and biocompatibility, it is characterized in that: described lactic acid composite material is the compound system of poly(lactic acid) and pearl powder, pearl powder in the inside of poly(lactic acid) and surface uniform dispersion, and is exposed to surface and fully contacts with external environment.
2. a kind of lactic acid composite material promoting osteogenesis and biocompatibility according to claim 1, is characterized in that, the total amount of pearl powder is 1 ~ 50wt% of described lactic acid composite material.
3. a kind of lactic acid composite material promoting osteogenesis and biocompatibility according to claim 1, is characterized in that, described pearl powder is the pearl powder through polyoxyethylene glycol surface modification.
4. a kind of lactic acid composite material promoting osteogenesis and biocompatibility according to claim 1, is characterized in that, described lactic acid composite material is film, and thickness is 80 ~ 200 μm.
5. a kind of preparation method promoting the lactic acid composite material of osteogenesis and biocompatibility as claimed in claim 1, is characterized in that comprising the following steps:
(1) the surface activation process of pearl powder;
Pearl powder is joined in deionized water, adds polyoxyethylene glycol powder simultaneously, stir and ultrasonic after, freezing at-15 ~-20 DEG C, then lyophilize, obtains the pearl powder through polyoxyethylene glycol surface modification;
(2) preparation of lactic acid composite material;
Poly(lactic acid) is dissolved and is configured to solution in a solvent, then will add in solution through poly ethyldiol modified pearl powder, through stirring and after supersound process, being cast to after in sheet glass or watch-glass, remove solvent;
Be immersed in by poly(lactic acid)/pearl powder mixture with Partial digestion poly(lactic acid) surface in NaOH solution, clean oven dry, obtains lactic acid composite material.
6. preparation method according to claim 5, is characterized in that, the particle size of pearl powder is 100 ~ 400nm; The polymerization degree of polyoxyethylene glycol is 4000 ~ 10000Da; Polyoxyethylene glycol and pearl powder mass ratio are 2:98 ~ 5:95, the two quality and with deionized water quality than for 1:10 ~ 1:20; Described stirring also ultrasonicly refers to that stir speed (S.S.) is 500 ~ 1000rpm, ultrasonic power 40 ~ 50KHz, and the time is respectively 0.5 ~ 1h, obtains the homodisperse solution of pearl powder; The described freezing time is 12 ~ 15h; Described lyophilize is at-55 ~-45 DEG C, used time 20 ~ 24h.
7. preparation method according to claim 5, is characterized in that, poly(lactic acid) weight-average molecular weight is 70000 ~ 200000; Described solvent is trichloromethane or Isosorbide-5-Nitrae dioxane; Poly(lactic acid) is dissolved and is configured to the solution that massfraction is 5-10wt% in a solvent; To add in solution through poly ethyldiol modified pearl powder, pearl powder concentration is 1 ~ 50wt%; Described stirring and supersound process refer to that stir speed (S.S.) is 800 ~ 1000rpm and ultrasonic power 40 ~ 50KHz, and the time is respectively 0.5 ~ 1h;
8. preparation method according to claim 5, is characterized in that, then described removal solvent puts into 50 ~ 60 DEG C of vacuum drying oven 10-12h, to remove residual solvent after referring to and place 10 ~ 12h under room temperature environment.
9. preparation method according to claim 5, is characterized in that, the mass concentration of NaOH solution is 1 ~ 2M, and soak time is 10 ~ 20min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104910597A (en) * | 2015-05-08 | 2015-09-16 | 常州龙骏天纯环保科技有限公司 | Preparation method of active antibiotic biodegradable composite material |
| CN107163527A (en) * | 2017-07-12 | 2017-09-15 | 四川理工学院 | A kind of multiple material of bio-based bone engineering and 3D printing adhesive tape and its product |
| CN108324994A (en) * | 2018-04-26 | 2018-07-27 | 海口市人民医院（中南大学湘雅医学院附属海口医院） | Pearl powder artificial bone and preparation method thereof |
| CN109806438A (en) * | 2019-03-14 | 2019-05-28 | 广西大学 | A kind of orthopaedics adhesive and preparation method with promotion bone uptake function |
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| CN102357262A (en) * | 2011-10-09 | 2012-02-22 | 清华大学 | Porous composite scaffold of PLLA (polylactic acid)/pearl powder and its preparation method |
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| CN102357262A (en) * | 2011-10-09 | 2012-02-22 | 清华大学 | Porous composite scaffold of PLLA (polylactic acid)/pearl powder and its preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910597A (en) * | 2015-05-08 | 2015-09-16 | 常州龙骏天纯环保科技有限公司 | Preparation method of active antibiotic biodegradable composite material |
| CN107163527A (en) * | 2017-07-12 | 2017-09-15 | 四川理工学院 | A kind of multiple material of bio-based bone engineering and 3D printing adhesive tape and its product |
| CN108324994A (en) * | 2018-04-26 | 2018-07-27 | 海口市人民医院（中南大学湘雅医学院附属海口医院） | Pearl powder artificial bone and preparation method thereof |
| CN108324994B (en) * | 2018-04-26 | 2020-12-01 | 海口市人民医院（中南大学湘雅医学院附属海口医院） | Preparation method of artificial bone of pearl powder |
| CN109806438A (en) * | 2019-03-14 | 2019-05-28 | 广西大学 | A kind of orthopaedics adhesive and preparation method with promotion bone uptake function |
| CN109806438B (en) * | 2019-03-14 | 2021-10-26 | 广西大学 | Orthopedic adhesive with function of promoting bone growth and preparation method thereof |
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