CN102357262A - Porous composite scaffold of PLLA (polylactic acid)/pearl powder and its preparation method - Google Patents
Porous composite scaffold of PLLA (polylactic acid)/pearl powder and its preparation method Download PDFInfo
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- CN102357262A CN102357262A CN2011103035954A CN201110303595A CN102357262A CN 102357262 A CN102357262 A CN 102357262A CN 2011103035954 A CN2011103035954 A CN 2011103035954A CN 201110303595 A CN201110303595 A CN 201110303595A CN 102357262 A CN102357262 A CN 102357262A
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Abstract
Belonging to the technical field of biomedical materials, the invention discloses a porous composite scaffold of PLLA/pearl powder and its preparation method. The scaffold matrix is PLLA, and pearl powder is uniformly distributed inside and outside scaffold pore walls. characterized by porosity, the scaffold has an average pore size is 80-100 micrometers and average porosity of over 80%. The invention also discloses a preparation method of a PLLA/pearl powder scaffold. By making use of good biocompatibility and good osteogenesis of nacre, as well as the characteristic of self-carried bioactive factors, the invention prepares a signal factor-carrying porous composite scaffold of PLLA/pearl powder by means of blending and freeze drying methods. The preparation method is simple and practical, and the composite scaffold has good biocompatibility and good mechanical properties.
Description
Technical field
The invention belongs to the bio-medical material technical field, particularly porous compound support frame of PLLA/Margarita powder and preparation method thereof.
Background technology
At present, the research of porous compound support frame mainly concentrates on biodegradable macromolecule.A kind of biodegradable macromolecule-PLLA (PLLA) has excellent biological compatibility, biological degradability and mechanical property preferably, and controllable degradation property and machinability, its catabolite lactic acid can be participated in the metabolism of human body.This makes it become in the current biomedical sector one of the most valued material, and has been used for human body by united states drug food control office (FDA) approval.Polylactic acid and copolymer thereof are mainly used in controlled drug delivery system, bone inside-fixture, tissue repair and cell culture material and medical operation suture thread etc.But there is the defective of some application facet in PLLA: (1) polylactic acid is a lyophobic dust, has reduced its biocompatibility; (2) sour environment that causes of its catabolite quickens the degraded of PLLA self, also is prone to cause aseptic inflammation in the body; (3) as porous support, its mechanical property is not good.
Therefore, to the bone reparation, porous compound support frame both must keep certain mechanical property, can overcome the acid problem that PLLA causes again, was a problem with challenge.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art; The object of the present invention is to provide porous compound support frame of PLLA/Margarita powder and preparation method thereof; When improving pure PLLA porous support mechanical property, degradability, increase bioactie agent, and its preparation is simple and convenient.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of porous compound support frame of PLLA/Margarita powder, said support has porous, and matrix is a PLLA, and Margarita powder is evenly distributed on inside and outside the support hole wall.
The viscosity of said PLLA is 0.5-7.0dl/g.
The mean diameter of said Margarita powder is 10-100 μ m.
The mass ratio of said Margarita powder and PLLA is 0.01-99.
Said Margarita powder is from fresh water Margarita that hydriopsis cumingii produces, and Margarita is aragonite Margarita and ball aragonite Margarita.
Said support average pore size is 80-100 μ m, and the brace aperture rate is 80%-95%.
The present invention also provides the method for preparing of the porous compound support frame of said PLLA/Margarita powder, may further comprise the steps:
The first step is dissolved in organic solvent with PLLA, and mass volume ratio is 0.01-0.5g/ml, stirring and dissolving;
In second step, adding is the Margarita powder of 0.01-99 with the PLLA mass ratio again, stirring reaction 0.02-2 hour, and ultra-sonic dispersion 0.02-2 hour;
The 3rd step, pour second solution that obtains of step into mould, shake up 0.01-10 minute after, be placed on and be lower than in the zero degree environment precooling 2-24 hour;
In the 4th step, the sample that freezes is placed on and is lower than in the zero degree environment after lyophilization 12-96 hour, obtains exsiccant porous compound support frame.
Wherein, said organic solvent is the 1-4-dioxane, and said Margarita powder is aragonite Margarita powder and ball aragonite Margarita powder.
Wherein, aragonite and ball aragonite Margarita are used alcohol-pickled cleaning, the reuse deionized water is given a baby a bath on the third day after its birth all over the back natural drying.Use Chinese medicine grinder grinding and sieving (300 order) then, obtain the Margarita powder granule.
Prepared PLLA/Margarita powder the support of the present invention has significant advantage:
(1) excellent biological compatibility.PLLA that this compound rest is selected for use and Margarita powder all have excellent biological compatibility.Both compound uses, support also has excellent biological compatibility.
(2) add Margarita powder in right amount after, do not influence pattern, aperture and the porosity of PLLA support.The porous pattern and the certain aperture that keep support help cell attaching, propagation and differentiation.Simultaneously, behind the interpolation Margarita powder, can increase the mechanical property of support.
(3) good bone inductive effect.After adding Margarita powder,, have bone conductibility and ossification preferably, be easy to skeletonization in stent area because physics, chemical property and biological characteristics and the osseous tissue of nacreous layer are very approaching.The self-contained bioactie agent of Margarita powder, and signal factor is comparatively stable in nacreous layer, changeableness not plays the effect of slow release.
(4) method for preparing is simple.Carry atopen or proteic support often in order to ensure proteic slow release and not changeableness and complicated process of preparation; And PLLA/Margarita powder support utilizes signal factor stability in nacreous layer; Only need to be added into Margarita powder that lyophilization gets final product in the solution of PLLA, the preparation process is the stick signal factor more simply more intactly.
(5) alleviate the acid problem that the PLLA degraded causes.Acid mass-energy and calcium carbonate that the PLLA degraded produces react.Simultaneously, aragonite Margarita powder and ball aragonite Margarita powder are alkalescence in external degradation, and PLLA/aragonite support, PLLA/ball aragonite support also are alkalescence in external degradation.Alkaline environment can in the acidity that causes with PLLA degraded, stablize the pH value of microenvironment, help the growth and the propagation of cell, the elongate composite scaffold degradation time.
Description of drawings
Fig. 1 is PLLA of the present invention/aragonite Margarita powder support cross section shape appearance figure;
Fig. 2 is PLLA of the present invention/ball aragonite Margarita powder support cross section shape appearance figure;
Fig. 3 is the distribution shape appearance figure of PLLA of the present invention/ball aragonite Margarita powder support Margarita powder.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is explained further details.
Embodiment 1: a kind of PLLA of composition/aragonite Margarita powder support
The preparation process is following:
The first step is dissolved in 0.4g PLLA (mean molecule quantity 100KDa) in the 1-4-dioxane of 8mL, magnetic agitation 8h, the 1-4-dioxane solution of formation 5% (w/v) PLLA;
In second step, the aragonite Margarita with alcohol-pickled 4 hours, is given a baby a bath on the third day after its birth all over the back natural drying with deionized water then; Reuse Chinese medicine grinder grinding and sieving (300 order) obtains aragonite Margarita powder granule, gets in the solution of the 0.4g aragonite Margarita powder adding first step; Continue to stir 0.5h, with the intensity ultra-sonic dispersion 0.5h of 60w, make even mixed solution then; Wherein, the mass ratio of PLLA and aragonite Margarita powder is 1: 1.
The 3rd the step, pour solution into cylinder mold, shake up 5 minutes after, be placed on freezing 12 hours of-20 ℃ of environment.
The 4th step, the sample that freezes is put into freezer dryer, wherein, more than-60 ℃ of pre-cooling 0.5h, lyophilization obtains exsiccant porous compound support frame to freezer dryer after 72 hours.
Gained PLLA/aragonite Margarita powder support cross section pattern is as shown in Figure 1, average pore size 80-100 μ m, and porosity 86.4%, average yield strength are 0.550MPa.
Embodiment 2: a kind of PLLA of composition/ball aragonite Margarita powder support
The preparation process is following:
The first step is dissolved in 0.4g PLLA (mean molecule quantity 100KDa) in the 1-4-dioxane of 8mL, magnetic agitation 8h, the 1-4-dioxane solution of formation 5% (w/v) PLLA;
In second step, ball aragonite Margarita with alcohol-pickled 4 hours, is given a baby a bath on the third day after its birth all over the back natural drying with deionized water then; Reuse Chinese medicine grinder grinding and sieving (300 order) obtains ball aragonite Margarita powder granule, gets in the solution of the 0.6g ball aragonite Margarita powder adding first step; Continue to stir 0.5h, with the intensity ultra-sonic dispersion 0.5h of 60w, make even mixed solution then; Wherein, the mass ratio of PLLA and ball aragonite Margarita powder is 2: 3.
The 3rd the step, pour solution into cylinder mold, shake up 5 minutes after, be placed on freezing 12 hours of-20 ℃ of environment.
The 4th step, the sample that freezes is put into freezer dryer, wherein, more than-60 ℃ of pre-cooling 0.5h, lyophilization obtains exsiccant porous compound support frame to freezer dryer after 72 hours.
Gained PLLA/ball aragonite Margarita powder support cross section pattern is as shown in Figure 2, average pore size 80-100 μ m, and porosity 87.9%, average yield strength are 0.601MPa, the distribution pattern of Margarita powder is as shown in Figure 3.
The PLLA of 3: two kinds of compositions of embodiment/Margarita powder compound rest
The preparation process is following:
The first step is dissolved in 0.4g PLLA (mean molecule quantity 100KDa) in the 1-4-dioxane of 8mL, magnetic agitation 8h, the 1-4-dioxane solution of formation 5% (w/v) PLLA;
Second step, with 0.26g aragonite Margarita and 0.17g ball aragonite Margarita with alcohol-pickled 4 hours, then with the deionized water natural drying time afterwards of giving a baby a bath on the third day after its birth; Reuse Chinese medicine grinder grinding and sieving (300 order) obtains mixing the Margarita powder granule, gained mixing Margarita powder is added in the solution of the first step; Obtain aragonite Margarita powder content and be 40%, ball aragonite Margarita powder content is the mixed solution of 30% (w/w); Stir 0.5h, with the intensity ultra-sonic dispersion 0.5h of 60w, make even mixed solution then.
The 3rd the step, pour solution into cylinder mold, shake up 5 minutes after, be placed on freezing 12 hours of-20 ℃ of environment.
The 4th step, the sample that freezes is put into freezer dryer, wherein, more than-60 ℃ of pre-cooling 0.5h, lyophilization obtains the porous compound support frame of exsiccant two kinds of compositions to freezer dryer after 72 hours.
Among the present invention,, select the granule that is added with biological activity and has certain mechanical property in order to improve the mechanical property of porous compound support frame.Adopt calcium carbonate also to carry signal factor, i.e. Margarita powder is with the compound preparation porous support of PLLA.Research shows that calcium carbonate has excellent biological compatibility, compares with calcium phosphate, and less stable, dissolubility is better.The physics of nacreous layer, chemical property and biological characteristics and osseous tissue are very approaching.Nacreous layer has reduced immunogenicity, excellent biological compatibility, degradability, bone conductibility and ossification preferably, and self-contained bioactie agent, meets the design concept of ideal timbering material.The somatomedin that contains in the organic substrate of nacreous layer, as if the albumen of soluble small-molecular weight is for the differentiation that promotes osteocyte with breed even more important in the organic substrate.
Natural mussel pearl can be divided into aragonite Margarita and ball aragonite Margarita, and research shows that pure ball aragonite Margarita internal structure is loose, and stability is poor than aragonite.Though both water soluble substrate is not quite identical, ball aragonite pearl organic matrix content is a little more than the aragonite Margarita.Therefore can know that ball aragonite Margarita might be higher than aragonite Margarita degradation rate, osteoinductive is strong.So, prepare porous PLLA/Margarita powder timbering material with aragonite/ball aragonite Margarita, when improving the timbering material degradability, increase bioactie agent, be a kind of support preparation mode that has very much application prospect.
The sour environment that the PLLA catabolite causes quickens the degraded of self; Through experimental verification; Aragonite Margarita powder and ball aragonite Margarita powder are alkalescence in external degradation; PLLA/aragonite Margarita, PLLA/ball aragonite Margarita support also are alkalescence in external degradation, alkaline environment can in degraded causes with PLLA acidity.Stablize the pH value of microenvironment, help the growth and the propagation of cell, but also elongate composite scaffold degradation time.
More than among each embodiment:
The mean diameter assay method of Margarita powder: laser particle size analyzer (Mastersizer 2000, Britain) is measured its mean diameter.
The method of testing of porosity: test three groups of samples respectively with mercury injection apparatus (Autopore IV9510, the U.S.) and average.
The method of testing of yield strength: (Zwick Z005, Germany) tests and draws stress-strain diagram with omnipotent mechanical test appearance, and the starting point from linear deformation to the plastic deformation can be considered yield strength value.Testing three groups of samples averages.
Degraded solutions generally adopts phosphate buffer (PBS solution), because calcium carbonate and the biphosphate reactant salt among the PBS in the support, so select for use 0.9% sodium chloride solution as degraded solutions.
In the preparation process of the present invention, parameters of choice is more wide in range, and the amount ratio of PLLA and organic solvent can satisfy the dissolving demand and follow-up Margarita powder disperses to get final product; And the amount ratio of PLLA and Margarita powder then almost can be any ratio, according to different application environments; Generally in the scope of 99-0.01, choose; Lyophilization then will make till the support finish-drying, therefore, parameter rationally and optimized choice be not to be understood that and be limitation of the present invention.
Claims (10)
1. the porous compound support frame of a PLLA/Margarita powder is characterized in that, said support has porous, and matrix is a PLLA, and Margarita powder is evenly distributed on inside and outside the support hole wall.
2. the porous compound support frame of PLLA/Margarita powder according to claim 1 is characterized in that, the viscosity of said PLLA is 0.5-7.0dl/g.
3. the porous compound support frame of PLLA/Margarita powder according to claim 1 is characterized in that, the mean diameter of said Margarita powder is 10-100 μ m.
4. the porous compound support frame of PLLA/Margarita powder according to claim 1 is characterized in that, the mass ratio of said Margarita powder and PLLA is 0.01-99.
5. the porous compound support frame of PLLA/Margarita powder according to claim 1 is characterized in that, said Margarita powder is from fresh water Margarita that hydriopsis cumingii produces.
6. the porous compound support frame of PLLA/Margarita powder according to claim 5 is characterized in that, said Margarita is aragonite Margarita and ball aragonite Margarita.
7. the porous compound support frame of PLLA/Margarita powder according to claim 1 is characterized in that, said support average pore size is 80-100 μ m.
8. the porous compound support frame of PLLA/Margarita powder according to claim 1 is characterized in that, said brace aperture rate is 80%-95%.
9. the method for the porous compound support frame of the said PLLA/Margarita powder of preparation claim 1 is characterized in that, may further comprise the steps:
The first step is dissolved in organic solvent with PLLA, and mass volume ratio is 0.01-0.5g/ml, stirring and dissolving;
In second step, adding is the Margarita powder of 0.01-99 with the PLLA mass ratio again, stirring reaction 0.02-2 hour, and ultra-sonic dispersion 0.02-2 hour;
The 3rd step, pour second solution that obtains of step into mould, shake up 0.01-10 minute after, be placed on and be lower than in the zero degree environment precooling 2-24 hour;
In the 4th step, the sample that freezes is placed on and is lower than in the zero degree environment after lyophilization 12-96 hour, obtains exsiccant porous compound support frame.
10. method according to claim 9 is characterized in that, said organic solvent is the 1-4-dioxane, and said Margarita powder is aragonite Margarita powder and ball aragonite Margarita powder.
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Cited By (8)
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| CN102949753A (en) * | 2012-11-26 | 2013-03-06 | 中国人民解放军第四军医大学 | Porous composite bracket and preparation method thereof |
| CN104027840A (en) * | 2014-06-16 | 2014-09-10 | 清华大学 | Preparation method of porous scaffold for bone repair |
| CN104592725A (en) * | 2014-12-25 | 2015-05-06 | 东华大学 | Polylactic acid composite material for promoting bone growth and biocompatibility and preparation method of polylactic acid composite material |
| CN105343936A (en) * | 2015-11-05 | 2016-02-24 | 深圳市第二人民医院 | Poly-L-lactide-caprolactone copolymer (PLCL) three-dimensional porous scaffold, PLCL and collagen (PLCL-COL) composite scaffold and preparation methods of scaffolds |
| CN106668953A (en) * | 2017-01-05 | 2017-05-17 | 上海理工大学 | Preparation method of pearl powder-calcium sulfate compound bone tissue engineering bracket |
| CN107185048A (en) * | 2017-06-28 | 2017-09-22 | 海口市人民医院 | The preparation method of Nano pearl powder/C HA compound rests |
| CN107261215A (en) * | 2017-06-28 | 2017-10-20 | 海口市人民医院 | Nano pearl powder/C HA compound rests and its application |
| CN109260521A (en) * | 2018-10-16 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of degradable artificial bone and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109260521A (en) * | 2018-10-16 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of degradable artificial bone and preparation method thereof |
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Application publication date: 20120222 |