CN102557398A - Boron-containing nano-mesoporous and macroporous bioactive glass, and preparation method and application thereof - Google Patents
Boron-containing nano-mesoporous and macroporous bioactive glass, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a boron-containing nano-mesoporous and macroporous bioactive glass, a preparation method thereof and the application thereof to medical supports. The boron-containing mesoporous bioactive glass is prepared by substituting BO33- for part of SiO44- by a sol-gel method. According to the method, controllable porosity (78 to 90 percent) is obtained by adjusting immersion times (2 to 5 times) and aperture (300 to 500 microns). The composite glass material has pores suitable for cell growth; tissue growth and nutrition transmission are facilitated due to the porosity characteristic; and the structural integrity of the supports can be maintained in vitro. When the boron content is 0 to 10 percent, the boron-containing ordered mesoporous bioactive glass support has large surface area of 365 to 194 m<2>/g and is suitable for serving as vectors of medicines and growth factors. The biological material can slowly release boron ions, can serve as a tissue repair material applied to bone and periodontium engineering, and can serve as vectors of medicines or genes.
Description
Technical field
The present invention relates to big hole bioactive glass material of mesoporous nano of a kind of boracic and preparation method thereof, belong to biomedical materials field.
Background technology
Mesopore bioactive glass (MBG) as a kind of biological active materials, has caused great concern in recent years.Characteristics that showing of the more non-mesopore bioactive glass of mesopore bioactive glass (NBG) are that it has specific surface area and the nanoporous volume that significantly improves, thereby have obtained more excellent phosphatic rock mineralization ability and degradation property.We prove recently, CaO-P
2O
5-SiO
2System MBG can improve external and intravital biological activity and degraded, medicine carrying ability than NBG.As a kind of biological active materials, MBG shows great potential in bone tissue engineer and pharmaceutical carrier application.For this reason, a kind of MBG with best composition and nanostructure of exploitation ten minutes is meaningful.In addition, suitable medicine carrying can improve the osteogenic ability of MBG, in bone tissue engineer, uses to have big potentiality.
Boron is one of trace element of human body, in many vital processes, comprises embryo, skeletal growth and maintenance, plays an important role in immunologic function and the psychomotor skill.Particularly in postmenopausal women, boron possibly stimulate hormone, thereby through stimulating estrogenic secretion to reach the estrogenic effect of simulation.At present, estrin treatment is to prevent deossification after the menopause and the osteoporosis that causes and bone density reduce one of effective means of the fracture that causes.Therefore, the researchist becomes the focus of research in bone health and regeneration field to the development of the biological active materials that is loaded with boron.So far, the research that is used for bone tissue engineer about the mesoporous glass supporter of boracic does not appear in the newspapers.
In bone tissue engineer, growth factor such as Delicious peptide (BMP-2 and BMP-7) are written into support, with the growth of irritation cell differentiation and tissue.Yet bone morphogenetic protein is quite expensive, and must under condition as mild as a dove, combine to prevent its bioactive loss with support.For overcoming this drawback, a kind of alternate method is to be used for stimulating bone growth through the osteoblast differentiation medicament.DEXAMETHASONE BP98 (DEX) is a kind of traditional skeletonization medicine, is used for cell culture experiments, inducing cell propagation, ripe and osteoblastic mineralization of extracellular matrix.Before this, DEXAMETHASONE BP98 is loaded and gathers that (lactic acid-ethanol, PLGA) microballoon, PLGA and polycaprolactone (PCL) are that bone tissue engineering scaffold is used.These polymkeric substance have the insufficient shortcoming of bone conductibility as bone renovating material, and always need add bioactive inorganic materials preparation becomes matrix material.And traditional biological active ceramic and glass (Win 40350, tricalcium phosphate, bio-vitric) support lacks medicine carrying ability efficiently.
Summary of the invention
First purpose of the present invention is to provide a kind of mesoporous nano and macropore composite bioactivity glass material of boracic;
Second purpose of the present invention is to provide above-mentioned bioactivity glass preparation methods;
The 3rd purpose of the present invention is to provide the purposes of above-mentioned bioactivity glass material.
Be to realize that above-mentioned purpose, bioactivity glass material provided by the invention have macropore and about 5nm mesoporous of 300 μ m-500 μ m, its boron-containing quantity is 0% ~ 10% (greater than 0).Wherein the porosity of macropore is 78%-90%, and mesoporous pore volume is at 0.21-0.33cm
3/ g, the aperture is about 5nm.
The matrix of above-mentioned glass material can be existing any glass material that can be used for support.
The macropore of bioactivity glass material of the present invention is fit to the cell growth, and mesoporous nano then is suitable for the release of medicine carrying control medicine, can discharge the boron ion simultaneously, can be used as carrier or medical support.For example can be used as medicine or genophore, be used to load DEXAMETHASONE BP98, growth factor, be not limited to these medicines again, can be used as the long-time effectively slowly-releasing of slow releasing carrier of medication, be applied to the three-dimensional rack of bone defect repair packing material or organizational project.
Bioactivity glass material of the present invention is through in the process of preparation mesopore bioactive glass, uses BO3
3-Replace part Si O4
4-, synthesize the ordered mesopore bioactive glass of boracic through the preparation method of gel sol method.This method comprises following step:
(1) template, boron source, calcium source, phosphorus source, silicon source are dissolved in ethanol, 18 ℃-45 ℃ are stirred 12-48h down, obtain gel; The content of boron has direct influence for meso-hole structure afterwards;
(2) the polymer sponge was immersed gel 10-60 minute that obtains, changed sponge over to another container, dry 12-48h;
(3) after to be dried, 600 ~ 800 ℃ of calcinings 3-8 hour obtain the mesoporous nano and the macropore compound bio glass material of boracic.
In the aforesaid method, step 2) can repeat 2-5 time.
Template can be to be nonpolar triblock copolymer body template in the aforesaid method; Main article EO20PO70EO20 (P123) by name; EO106PO70EO106 (F127) and EO39BO47EO39 (B50 – 6600), but be not limited to these several kinds, as structure directing agent.EO is a polyethylene oxide, and PO is a polypropyleneoxide, and BO is the polybutylenes oxidation.Template is according to adding with weight ratio 1:1 ~ 3 of boron source, calcium source, silicon source, phosphorus source total amount.
In the aforesaid method, said boron source is preferably tributyl borate, and said silicon source is preferably tetraethoxy (TEOS), said calcium source is preferably Ca (NO
3)
24H
2O or CaCl
2, said phosphorus source is preferably triethyl phosphate.
In the aforesaid method, the mol ratio in described boron source, calcium source, phosphorus source, silicon source is preferably (0-10): (10-30): (1-10): (50-90).
Ethanol described in the aforesaid method is added doubly according to 4 ~ 16 of solute weight and is added.
The preparation method of the big hole bioactive glass of boracic mesoporous nano in the aforesaid method, the exsiccant method is for passing through heat drying or evaporation self-assembly.
The big hole bioactive glass of boracic mesoporous nano of the preparation in the aforesaid method, the content of boron is between 0%-10%.
Polymer sponge such as polyurethane sponge have different hole density (20ppi-80ppi) and are used to obtain (wide aperture: the hundreds of micron), big hole.
Non-ionic type block polymer collaboration template is that to be used to produce meso-hole structure (mesoporous: some nanometers).
The B-MBG of the present invention's preparation also has the ability that discharges boron and loading and slow releasing pharmaceutical except having macropore (300 μ m-500 μ m) and order mesoporous (5 nanometer).The present invention uses non-ionic type block polymer collaboration template and polymer sponge, uses BO3
3-Replace part Si O4
4-, this kind method can obtain controlled porosity (78%-90%) through the size (300 μ m-500 μ m) in adjustment submerged number of times (2-5 time) and aperture.These porosity characteristic frames help tissue and grow into and the nutrition transmission.The structural integrity that can keep them at external support.In the application of bone tissue engineer,, the main effect of these supports supports that they must be powerful in the cell cultures that is enough to handle because providing initial cell machinery.In this respect, the frame of B-MBG can satisfy the requirement as cell carrier in the bone tissue engineer.
Simultaneously, because the meso-hole structure of biomaterial is important to loading and transport the medicine ten minutes, surface-area is 200-350 m usually
2/ g, mesoporously organism-absorbing bioactive molecule such as medicine, microbiotic and growth factor can be provided for about 5nm.When boron content from 0 to 10% did not wait, the B-MBG support had 194-265 m
2The high surface-area of/g is suitable as the carrier of medicine and growth factor.
Description of drawings
The microstructure figure of the sample of the embodiment of the invention 1,2 preparations that Fig. 1 ESEM is taken, and with sample contrast with the not boracic of condition preparation.Wherein scheming a, b, c is respectively 0B-MBG, 5B-MBG and 10B-MBG.
Fig. 2 maller angle X diffraction is observed the mesoporous glass of boracic of embodiment 1,2 preparations, and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2.
Fig. 3 wide angle X diffraction is observed the mesoporous glass of boracic of embodiment 1,2 preparations, and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2.
The microstructure figure of the sample of the embodiment of the invention 2,3,4 preparations that Fig. 4 ESEM is taken.The a porosity is 90%, and the b porosity is that 86% c porosity is 78%.
Fig. 5 transmission electron microscope observing embodiment 2, and with sample contrast with the not boracic of condition preparation.A is with the mesoporous bioglass material of the not boracic of condition preparation; B embodiment 2.
Fig. 6 embodiment 1,2 puts into human body simulation body fluid (SBF), 0-3 days B, Ca, Si, P ionic discharge, and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2.
Fig. 7 embodiment 1,2 puts into before the human body simulation body fluid (SBF) and the comparison with energy spectrum analysis of ESEM afterwards, and contrasts with sample with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2.
Fig. 8 boron content is to the loading of medicine and the influence of release.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2.The DEXAMETHASONE BP98 stowage capacity of a different boron content.Ordinate zou is represented the efficiency of loading of DEX, and X-coordinate is represented the support of 3 kinds of different boron content.The release of the DEXAMETHASONE BP98 of b different boron content.Ordinate zou is represented the cumulative release per-cent of DEX, and X-coordinate is represented time of releasing.
Fig. 9 macropore porosity is to the loading of medicine and the influence of release.90 to represent macro porosity led be that 90%, 86 to represent macro porosity led be that 86%, 78 to represent macro porosity led be 78%.The DEXAMETHASONE BP98 stowage capacity of the different macro porosity led of a.Ordinate zou is represented the efficiency of loading of DEX, and X-coordinate is represented the support of 3 kinds of different macro porosity led.The release of the DEXAMETHASONE BP98 of the different macro porosity led of b.Ordinate zou is represented the cumulative release per-cent of DEX, and X-coordinate is represented time of releasing.
Figure 10 scleroblast is inoculated in embodiment 1,2, and ESEM is the growing state of cell on support after take 1 day and 7 days, and contrasts with sample with the not boracic of condition preparation.A b scleroblast is incubated at the glass 1 of the not boracic of condition preparation and 7 days ESEM picture; C d scleroblast is incubated at the ESEM picture of embodiment 1,1 and 7 days; C d scleroblast is incubated at the ESEM picture of embodiment 2,1 and 7 days
Figure 11 Oesteoblast growth on embodiment 1, embodiment 2 and embodiment 5,1,7,14 propagation situation in the sky, and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2, and DEX-10B-MBG is for loading embodiment 2 bioglass materials of DEXAMETHASONE BP98 (DEX).
Figure 12 Oesteoblast growth on embodiment 1, embodiment 2 and embodiment 5,7 days and 14 days alkaline phosphatase activities situation, and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2, and DEX-10B-MBG is for loading embodiment 2 bioglass materials of DEXAMETHASONE BP98 (DEX).
Figure 13 scleroblast is inoculated on the embodiment 1,2,5; 1 day and 7 days RT-qPCR detection type i collagens (a); Transcription factor Runx2 (b), the expression of SEAP ALP (c) and bone sialoprotein BSP (d), and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2, and DEX-10B-MBG is for loading embodiment 2 bioglass materials of DEXAMETHASONE BP98 (DEX).
Embodiment
Following examples are used to further specify the present invention, but should not be construed as limitation of the present invention.
The mol ratio in boron source, calcium source, phosphorus source, silicon source is with tributyl borate: Ca (NO
3)
24H
2O: triethyl phosphate: tetraethoxy, its mol ratio are 5:15:5:75, and the template addition is that 1/2 of aforementioned weight adds; Be dissolved in the ethanol of 8 times of weight, stirring at room 1 day, polyurethane sponge (25 PPI) was immersed in this solution 10 minutes after cleaning fully; Transfer to then in the petridish, remove excessive solution, remaining at room temperature evaporated 24 hours; This process repeats 2 times, in order to obtain the porosity of macropore support.Treat behind the sample complete drying 700 ℃ of calcinings 5 hours.
The mol ratio in boron source, calcium source, phosphorus source, silicon source is with tributyl borate: Ca (NO
3)
24H
2O: triethyl phosphate: tetraethoxy, its mol ratio are 5:15:2.5:70, and the template addition is 1/2 of boron source, calcium source, phosphorus source, a silicon source weight; Be dissolved in the ethanol of 10 times of weight parts, stirring at room 1 day, polyurethane sponge (25 PPI) was immersed in this solution 10 minutes after cleaning fully; Transfer to then in the petridish, remove excessive solution, remaining at room temperature evaporated 24 hours; This process repeats 2 times, in order to obtain the porosity of macropore support.Treat behind the sample complete drying 700 ℃ of calcinings 5 hours.
The MBG that contains 10% boron
The mol ratio in boron source, calcium source, phosphorus source, silicon source is with tributyl borate: Ca (NO
3)
24H
2O: triethyl phosphate: tetraethoxy, its mol ratio is 5:15:2.5:70, is dissolved in the ethanol; Stirring at room 1 day, polyurethane sponge (25 PPI) was immersed in this solution 10 minutes after cleaning fully, transferred in the petridish then; Remove excessive solution; Remaining at room temperature evaporated 24 hours, and this process repeats 3 times, in order to obtain the porosity of macropore support.Treat behind the sample complete drying 600 ℃ of calcinings 8 hours.
Embodiment 4 10B-MBG 5 times
The mol ratio in boron source, calcium source, phosphorus source, silicon source is with boron trioxide: quicklime: Vanadium Pentoxide in FLAKES: silicon-dioxide, its mol ratio are 5:15:2.5:70, with 0.5 M dissolving with hydrochloric acid in ethanol; Stirring at room 1 day, polyurethane sponge (25 PPI) was immersed in this solution 10 minutes after cleaning fully, transferred in the petridish then; Remove excessive solution; Remaining at room temperature evaporated 24 hours, and this process repeats 5 times, in order to obtain the porosity of macropore support.Treat behind the sample complete drying 800 ℃ of calcinings 3 hours.
The mesoporous characteristic of embodiment 5 different boron content relatively
Compare the bioglass material of different roc content is mesoporous, the result is as shown in table 1:
Table 1
| Material | Surface-area (m 2/g) | Pore volume (cm 3/g) | Aperture (nm) |
| 0B-MBG | 265 | 0.329 | 5.285 |
| 5B-MBG | 234 | 0.244 | 5.280 |
| 10B-MBG | 194 | 0.207 | 5.086 |
Surface-area (the m of the sample of table 1 embodiment 1,2
2/ g), pore volume (cm
3/ g) and the parameter of aperture (mm), and with sample contrast with the not boracic of condition preparation.The 0B-MBG representative is with the mesoporous bioglass material of the not boracic of condition preparation; 5B-MBG represents embodiment 1; 10B-MBG represents embodiment 2.
Bioglass material changes in the embodiment 6 simulated body fluid environment
DEXAMETHASONE BP98 (DEX) is dissolved in phosphate buffered saline buffer (PBS) in the ratio of 0.05 mg/ml.10B-MBG at room temperature was soaked in DEXAMETHASONE BP98/PBS liquid 24 hours, place then 40 ℃ following 24 hours, obtain to contain the mesoporous glass DEXAMETHASONE BP98 slow-released carrier (DEX-10B-MBG) of boron.
The medicine-releasing performance of DEX-10B-MBG is at first described.Under 37 ℃, the 10B-MBG that is loaded with DEX is put into 4ml phosphate buffered saline buffer (PBS), 6,24,72,120,192,360,528 hours, discharge through the ultra-violet analysis DEXAMETHASONE BP98.Calculate DEXAMETHASONE BP98 cumulative release rate (%) through following formula:
DEXAMETHASONE BP98 (%)=(the total drug loading of the DEXAMETHASONE BP98 release/DEXAMETHASONE BP98 of total charge on MBG) x100%.
Under the same terms 0B-MBG (not boracic), 5B-MBG (boracic 5%) are carried out above-mentioned experiment.
The result is shown in Fig. 8 and 9, and the adding of boron is to the loading and the not influence of release of the DEXAMETHASONE BP98 of support.The support of 86% and 90% porosity demonstrates high medicine stowage capacity, but it is discharged then not influence.
Get scleroblast, cell growth reaches 80 ~ 90% when converging, and with the digestion of 0.25% trypsin solution, the cell of digestion bounces back into bright sphere, after nutrient solution stops digestion, blows and beats gently cell is come off at the bottom of bottle.Get size and be the embodiment of 5x5x4 mm, place 48 orifice plates.The adjustment cell density is 1 * 10
7Individual/ml, draw the surface that 50 μ l cell suspensions slowly are added drop-wise to timbering material, be put in 37 ℃ of constant incubator static cultivation 3h that contain 5% CO2, in orifice plate, add the DMEM cell culture fluid 1.5ml of 10% FBS then.Changed one time cell culture fluid in per two days, cultivated 1 day and 7 days.After with the cytoskeleton mixture with PBS rinsing three times gently; Fix with 2.5% pentanedial liquid of precooling then, the alcohol dehydrated in successive sticks in the cytoskeleton mixture on the loading base station with double faced adhesive tape behind the CO2 critical point drying; Particle spraying appearance metal spraying is taken a picture with scanning electron microscopic observation after handling.The result is shown in figure 10, and cell is fusiformis, unfold fully, and nucleus place protuberance, the visible matrix of cell peripheral is adhered to.In brace aperture, can see the inwall that cell is attached at hole, and the part cell adheres to also between two adjacent apertures, the extracellular matrix components of emiocytosis also adhesion deposition in hole.
The cell culture processes of observation of cell situation of proliferation and differentiation on embodiment is the same, and be 1,3 and 7 day observing time, through the propagation situation and the differentiation situation of MTT reagent and ALP test kit observation of cell.Shown in figure 11, the cell proliferation of embodiment 4 is significantly higher than other groups, and the adding of boron has significantly improved the propagation of cell.Shown in figure 12, scleroblast expression of ALP there was no significant difference between each embodiment, the adding of boron does not have the pair cell differentiation influential, and the cell proliferation that is loaded with the embodiment of DEXAMETHASONE BP98 is significantly higher than the embodiment that is not loaded with DEXAMETHASONE BP98.
Observation of cell is incubated at the situation of genetic expression on the embodiment.Cell culture processes is the same; Observing time, point was 7 days and 14 days, and getting supernatant carries out real-time quantitative PCR analysis (realtime-PCR), and the result is shown in figure 12; The expression of embodiment 4 has significantly strengthened the scleroblast type i collagen the 7th day and 14 days; And the 7th day expression of Runx2 gene, simultaneously, the expression of the embodiment 4 that is loaded with DEXAMETHASONE BP98 has significantly strengthened scleroblast type i collagen, Runx2, SEAP and bone sialoprotein gene the 7th day and 14 days.
Above result shows that the mesoporous big hole bioactive glass of boracic has the potentiality of application aspect bone tissue engineer; Simultaneously, the mesoporous big hole bioactive glass of this boracic is with a wide range of applications aspect the bioengineered tissue as pharmaceutical carrier.
Claims (10)
1. method for preparing the mesoporous nano and the macropore compound bio glass material of boracic comprises:
A is dissolved in ethanol with template, boron source, calcium source, phosphorus source, silicon source; 18 ℃-45 ℃ were stirred 12-48 hour down; Obtain gel, wherein the mol ratio in boron source, calcium source, phosphorus source, silicon source is counted (0-10) with boron, calcium, phosphorus and element silicon: (10-30): (1-10): (50-90);
B immerses the polymer sponge gel 10-60 minute that obtains, and changes sponge over to another container, dry 12-48h;
After c is to be dried, calcined 3-8 hour for 600 ~ 800 ℃, obtain the mesoporous nano and the macropore compound bio glass material of boracic.
2. method according to claim 1 also comprises repeating step b) 2-5 time.
3. method according to claim 1 and 2, wherein said template are nonpolar triblock copolymer body template.
4. method according to claim 3, wherein said template are EO20PO70EO20, EO106PO70EO106 or EO39BO47EO39, and wherein EO representes polyethylene oxide, and PO representes polypropyleneoxide, and BO representes the polybutylenes oxidation.
5. method according to claim 1 and 2, wherein said boron source is a tributyl borate, said silicon source is that tetraethoxy, said calcium source are Ca (NO
3)
24H
2O or CaCl
2, said phosphorus source is a triethyl phosphate.
6. mesoporous nano and macropore compound bio glass material according to each described method preparation of claim 1 ~ 5.
7. bioglass material according to claim 6 is characterized in that the molar content of boron is between 0%-10%.
8. bioglass material according to claim 7 is characterized in that, said macropore diameter between 300-500 μ m, said mesoporous be 5nm.
9. each described mesoporous nano of claim 6 ~ 8 and the application of macropore compound bio glass material in medicine or genophore.
10. each described mesoporous nano of claim 6 ~ 8 and the application of macropore compound bio glass material in the three-dimensional rack of bone defect repair packing material or organizational project.
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