CN104368047B - High-intensitive multi-stage micro-nano structure silicon substrate bone renovating bracket material, preparation method and application - Google Patents
High-intensitive multi-stage micro-nano structure silicon substrate bone renovating bracket material, preparation method and application Download PDFInfo
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Abstract
The present invention relates to high-intensitive multi-stage micro-nano structure silicon substrate bone renovating bracket material, preparation method and applications.The present invention is added mesoporous silicon oxide microballoons reinforcing agent, prepares the multilevel structure timbering material with excellent mechanical performance using mesoporous silicon based xerogel as matrix.Silicon substrate bone renovating bracket material prepared by the present invention has both 200-500 μm be highly connected to, micron order macropore and 2-22nm mesoporous nano, and porosity is up to 60~90%, and mechanical property is up to 10MPa.Multi-stage micro-nano structure silicon substrate bone renovating bracket material of the invention may be used as bone tissue engineering scaffold and slow releasing carrier of medication etc..
Description
Technical field
The invention belongs to material science and medical domains；More particularly it relates to a kind of high strength, multistage knot
Silicon substrate composite bone repair stent material of structure and its preparation method and application.
Background technique
Disease, wound, aging of population and natural calamity etc. can lead to body bone tissue damage, clinically to Bone Defect Repari
Materials demand is huge.And as the operation of the autologous bone transplanting of Golden Rule since its source is limited and to patient's second operation pain
It is set much to be unable to satisfy status.There is also bio-safety potential problems for allogenic bone transplantation operation, may leave to patient throughout one's life
Immunological rejection and bring unidentified illness.Therefore, it manually prepares bone renovating material and clinically receives more and more passes
Note.
Due to good bioactivity, biological degradability and biocompatibility, silica-base material, such as bioactivity glass
Deng being widely used as osseous tissue renovating material.Especially mesoporous bioglass system, high specific surface area and pore volume make its table
Reveal more preferably biomineralization, biodegrade and drug/albumen controlled release ability, to have better osteogenic in vivo and in vitro
Can (Science, 2002;295:1014-1017).For the friendship of further satisfaction osteogenetic process nutriment, metabolic products
It changes and blood vessel, the needs of tissue grown into, promotion osteogenic activity, the structure that researcher simulates nature bone is constructed with macropore
With micropore multilevel structure timbering material, the inside and outside osteogenic activity of material is effectively improved.However, due to the spy of material itself
Point, have both micron macropore and mesoporous multilevel structure timbering material has notable defect in the following areas: 1. brittleness is big, Biological Strength
It is poor to learn performance, 2. molding is difficult, poor plasticity, and 3. material degradation is fast, system pH is caused to increase [ Microporous.Mesoporous
Materials143 (2011) 311-319, Acta Biomaterialia7 (2011) 2644-2650 ].Therefore, it is keeping/is changing
While kind micron-nanometer multi pore structure silicon substrate bone renovating bracket material advantage, the mechanical strength for improving timbering material is this
The ultimate challenge that field faces at present.
Currently, preparing the common method of porous support mainly has three classes: 1. hard template method: NaCl particle, PMMA/PS are micro-
Ball, being unable to get ideal connection macropore is the critical issue for limiting its utilization, and 2. 3D printing technique, accurately controls macroporous structure
And pattern, but the compound certain proportion polymeric additive of forming process palpus, its meso-hole structure and biology are influenced to a certain extent
Performance is learned, 3. polyurethane foam method, although process economy is easy to operate and the porous structure of high interconnected pore rate can be obtained, used
Repeatedly dip-squeeze-heat treatment preparation bracket mechanical property is bad at present, hole uniformity is poor, this directly affects its use
Effect.
Summary of the invention
The purpose of the present invention is to provide a kind of high strength, multilevel structure silicon substrate composite bone repair stent material and
Preparation method and application.
In the first aspect of the present invention, a kind of silicon substrate bone repairing support material with micron-nanometer multi pore structure is provided
Expect that there is 200-500 μm of micron order macropore and 2-22nm mesoporous nano, the timbering material packet in the timbering material
It includes:
100 parts by weight of mesoporous silicon based xerogel material；With
Mesoporous silicon oxide microballoons 5-40 parts by weight.
In a preferred embodiment, the silicon substrate bone renovating bracket material is substantially by mesoporous silicon based xerogel material 100
Parts by weight and mesoporous silicon oxide microballoons 5-40 parts by weight composition.
In another preferred example, the timbering material is prepared as follows:
(1) by 100 parts by weight of mesoporous silicon based xerogel material and mesoporous silicon oxide microballoons 5-40 parts by weight (preferably 5-
30 parts by weight are more preferably 5-20 parts by weight) mixing；
(2) by the mixture of (1) with 0.3-0.8g/1cm3(i.e. 1cm3Sponge is poured 0.3-0.8g；More preferably such as 0.7g/
1cm3、0.6g/1cm3、0.5g/1cm3) mass volume ratio be cast on polyurethane sponge, be aged, dry, calcining, obtaining institute
State timbering material.
In another preferred example, the mesoporous silicon oxide microballoons include but is not limited to: MCM-41, SBA-15, biology
Glass microsphere.
In another preferred example, the mesoporous silicon oxide microballoons are prepared as follows: by surfactant 1-10 parts by weight (compared with
Good ground 4-8 parts by weight) it is added to aqueous solvent (such as water or ethyl alcohol；Preferably 50-170 parts by weight, more preferably 80-120 weight
Part) in, less than 2, (preferably hydrochloric acid is 0.1-30 parts by weight to salt acid for adjusting pH；More preferably 0.1-20 parts by weight) in, it is living to surface
Property agent dissolution after be added four water-calcium nitrate 0.5-10 parts by weight (preferably 0.5-5 parts by weight), triethyl phosphate 0.1-10 weight
Part (preferably 0.4-5 parts by weight), ethyl orthosilicate 3-50 parts by weight (preferably 5-20 parts by weight)；24 are stirred at 35 ± 5 DEG C
±1h。
In another preferred example, the mesoporous silicon based xerogel material is prepared as follows: by surfactant 1-15 weight
Aqueous solvent (such as ethyl alcohol is added in part (preferably 4-10 parts by weight)；Preferably 40-150 parts by weight, more preferably 40-120 weight
Part), less than 2, (preferably hydrochloric acid is 0.1-5 parts by weight to salt acid for adjusting pH；More preferably 0.1-4 parts by weight) in, to surfactant
After being completely dissolved, four water-calcium nitrate 0.3-5 parts by weight (preferably 0.5-3 parts by weight), triethyl phosphate 0.1-4 parts by weight are added
(preferably 0.2-2 parts by weight) and ethyl orthosilicate 3-50 parts by weight (preferably 5-20 parts by weight)；At 35 ± 5 DEG C stirring 24 ±
Ageing to viscosity is (4-7) × 10 after 1h4MPa。
In another preferred example, the surfactant is selected from: cetyl trimethylammonium bromide (CTAB, traditional Chinese medicines),
P123(EO20PO70EO20, Sigma), F127 (EO106PO70EO106, Sigma).
In another aspect of the present invention, the preparation method of the silicon substrate bone renovating bracket material is provided, which comprises
(1) by 100 parts by weight of mesoporous silicon based xerogel material and mesoporous silicon oxide microballoons 5-40 parts by weight (preferably 5-
30 parts by weight are more preferably 5-20 parts by weight) mixing；
(2) by the mixture of (1) with 0.3-0.8g/1cm3(i.e. 1cm3Sponge is poured 0.3-0.8g；More preferably such as 0.7g/
1cm3、0.6g/1cm3、0.5g/1cm3) mass volume ratio be cast on polyurethane sponge, be aged, dry, calcining, obtaining institute
State timbering material.
In a preferred embodiment, the silicon substrate bone renovating bracket material is prepared as follows: 5-40 parts by weight (preferably 5-
30 parts by weight are more preferably 5-20 parts by weight) mesoporous inorganic microballoon is uniformly dispersed in 100 weight by way of physical doping
In part mesoporous silicon based xerogel material, by resulting complex sol with 0.3-0.8g/1cm3(such as 0.7g/1cm3、0.6g/1cm3、
0.5g/1cm3) mass volume ratio on being cast in polyurethane sponge, room temperature ageing and 60 ± 5 DEG C of drying 48 ± 6h, 600 ±
100 DEG C of 6 ± 2h of calcining obtain the timbering material.
In another aspect of the present invention, the purposes of the silicon substrate bone renovating bracket material is provided, bone tissue work is used to prepare
Journey (including Bone Defect Repari, bone collection) bracket；Be used to prepare drug, albumen, growth factor controlled release carrier；Or it is used to prepare cell
Cultivate bracket.
In another aspect of the present invention, the purposes of mesoporous silicon oxide microballoons is provided, is used to prepare with micron-nanometer multi hole
The silicon substrate bone renovating bracket material of structure；The mesoporous silicon oxide microballoons include but is not limited to: MCM-41, SBA-15, life
Object glass microsphere；Preferably, the mesoporous silicon oxide microballoons are prepared as follows: (preferably by surfactant 1-10 parts by weight
4-8 parts by weight) it is added to solvent (such as water or ethyl alcohol；Preferably 50-170 parts by weight, more preferably 80-120 parts by weight) in, hydrochloric acid
Adjusting pH, (preferably hydrochloric acid is 0.1-30 parts by weight less than 2；More preferably 0.1-20 parts by weight) in, it is dissolved to surfactant
Four water-calcium nitrate 0.5-10 parts by weight (preferably 0.5-5 parts by weight), triethyl phosphate 0.1-10 parts by weight are added (preferably afterwards
0.4-5 parts by weight), ethyl orthosilicate 3-50 parts by weight (preferably 5-20 parts by weight)；24 ± 1h is stirred at 35 ± 5 DEG C.
Other aspects of the invention are apparent to those skilled in the art due to this disclosure
's.
Detailed description of the invention
Fig. 1, high-intensitive multilevel structure compound rest photo (after calcining): embodiment 6-9.As shown in the figure for complex sol with
0.6g/1cm3The bracket that is obtained after being cast in polyurethane sponge and after following process of mass volume ratio.
Fig. 2, high-intensitive multilevel structure compound rest (0.6g/1cm3Mass volume ratio casting) SEM figure.(A) embodiment
8；(B) embodiment 13.
Fig. 3, high-intensitive multilevel structure compound rest (0.6g/1cm3Mass volume ratio casting) TEM figure.(A) embodiment
8；(B) embodiment 13.
Fig. 4, high-intensitive multilevel structure compound rest (0.6g/1cm3Mass volume ratio casting) impregnated in simulated body fluid
3d rear surface hydroxyapatite deposition SEM figure.(A) embodiment 8；(B) embodiment 16.
Fig. 5, mouse mesenchymal stem cell (rBMSCs) are in multilevel structure compound rest (0.6g/1cm3Quality volume
Than casting) surface cell compatibility.(A) embodiment 6-9；(B) embodiment 11-14.Wherein, Control indicates that no material is empty
The vigor of institute's inoculating cell on white orifice plate.
Fig. 6, mouse mesenchymal stem cell are in multilevel structure compound rest (0.6g/1cm3Mass volume ratio casting) table
SEM figure is sprawled in face adherency.(A) embodiment 8；(B) embodiment 13.
Fig. 7, mouse mesenchymal stem cell are in multilevel structure compound rest (0.6g/1cm3Mass volume ratio casting) table
The cell adherence in face is sprawled and is permeated.(A1-A3) embodiment 8, (B1-B3) embodiment 13.
Fig. 8, the critical defect of rabbit radius middle section 15mm are model, postoperative 2 weeks (2W), the X-ray of 12 weeks (12W) defective bones
Figure, the timbering material prepared using embodiment 8.
Specific embodiment
The invention discloses a kind of with high strength, has both the silicon substrate Bone Defect Repari branch of micron-nanometer multi pore structure
Frame material.The present invention, using sol-gel-cellular polyurethane foam method, passes through object using mesoporous silicon based xerogel material as matrix
Reason doped meso pore silicon oxide microballoon and the viscosity for controlling colloidal sol, once-cast just prepare the multistage with excellent mechanical performance
Structure stand material.The mechanical property of silicon substrate bone repairing support prepared by the present invention is up to 10MPa or more, and has micron big
Hole (200-500 μm) and mesoporous nano (2-22nm), high interconnected pore rate 50-95%.
The silicon substrate bone renovating bracket material of micron-nanometer multi pore structure and its preparation
The present invention with mesoporous silicon based xerogel material (mesoporous bioglass) be matrix, mesoporous silicon substrate as known in the art
Xerogel material can also be applied in the present invention, such as some sol-gel method mesoporous bioglass systems.As of the invention
Preferred embodiment, the mesoporous silicon based xerogel material can be to be prepared as follows: using ethyl alcohol as solvent；Salt acid for adjusting pH is 2
Below；Cetyl trimethylammonium bromide (CTAB), P123 (EO20PO70EO20)、F127(EO106PO70EO106) it can be used as table
Face activating agent prepares 2-22nm mesoporous silicon based xerogel material by sol-gal process and different hydrothermal treatment process.
Ethyl orthosilicate (TEOS), four water-calcium nitrate (Ca (NO3)24H2O), triethyl phosphate (triethyl phosphate, TEP) point
It is not used as the source of silicon, calcium, phosphorus in mesoporous silicon based xerogel material.Sol-gel designed by different calcium, phosphorus silicone content
Component may respectively be: 100%SiO2、90%SiO2-5%CaO-5%P2O5、85%SiO2-10%CaO-5%P2O5And 80%SiO2-15%
CaO-5%P2O5(mass fraction).
As the preferred embodiment of the present invention, the mesoporous silicon based xerogel material is prepared as follows: by surface-active
Agent is added in the alcohol solvent under acid condition, and after surfactant is completely dissolved, four water-calcium nitrate, triethyl phosphate is added
And ethyl orthosilicate；Stirred at 35 ± 5 DEG C be aged afterwards for 24 hours to viscosity be (4-7) × 104Pa.s。
As the preferred embodiment of the present invention, the mesoporous silicon based xerogel material is as containing component shown in table 1
Material is prepared.
Table 1
| Parts by weight | Preferable parts by weight | |
| Surfactant | 1-15 parts by weight； | 4-10 parts by weight |
| Aqueous solvent (such as ethyl alcohol) | 40-150 parts by weight | 40-120 parts by weight |
| Hydrochloric acid | 0.1-5 parts by weight | 0.1-4 parts by weight |
| Four water-calcium nitrate | 0.3-5 parts by weight | 0.5-3 parts by weight |
| Triethyl phosphate | 0.1-4 parts by weight | 0.2-2 parts by weight |
| Ethyl orthosilicate | 3-50 parts by weight | 5-20 parts by weight |
In material of the invention, mesoporous silicon oxide microballoons are added to enhance the mechanical property of bracket.The mesoporous oxygen
SiClx microballoon includes MCM-41, SBA-15, bio-vitric microballoon etc..Inorganic strengthening agent can be dispersed in mesoporous silicon backbone to coagulate
In glue material.Preferably, the mesoporous inorganic microballoon is prepared as follows: surfactant being added aqueous molten under acid condition
It in agent, stirs after surfactant is completely dissolved, addition four water-calcium nitrate, triethyl phosphate and ethyl orthosilicate, 35 ± 5 DEG C
Lower stirring is for 24 hours.
As the preferred embodiment of the present invention, the mesoporous silicon oxide microballoons are as the material containing component shown in table 2
It is prepared.
Table 2
| Parts by weight | Preferable parts by weight | |
| Surfactant | 1-10 parts by weight | 4-8 parts by weight |
| Water | 50-170 parts by weight | 80-120 parts by weight |
| Concentrated hydrochloric acid (ammonium hydroxide) | 0.1-30 parts by weight | 0.1-20 parts by weight |
| Four water-calcium nitrate | 0.5-10 parts by weight | 0.5-5 parts by weight |
| Triethyl phosphate | 0.1-10 parts by weight | 0.4-5 parts by weight |
| Ethyl orthosilicate: | 3-50 parts by weight | 5-20 parts by weight |
The mass ratio of preferred embodiment according to the present invention, the mesoporous silicon matrix and mesoporous silicon oxide microballoons is in 100:5-
40。
The present invention also provides the preparations of the silicon substrate bone renovating bracket material with micron-nanometer multi pore structure
Method, comprising: mix 100 parts by weight of mesoporous silicon based xerogel material and mesoporous silicon oxide microballoons 5-40 parts by weight；It will be mesoporous
The mixture of silicon based xerogel material and mesoporous silicon oxide microballoons is with 0.3-0.8g/1cm3Mass volume ratio be cast in poly- ammonia
It on ester sponge, is aged, dries, calcining, obtaining the timbering material.
Wherein, different enhancing agent content, different reinforcing agent types, polyurethane foam density and colloidal sol viscosity this be
The controllable Bone Defect Repari compound rest for preparing different mechanical strengths of column parameter；Simultaneously regulate and control synthesis condition (such as: solvent, pH,
Template, temperature) a variety of mesoporous materials with different specific surface areas, aperture can be prepared.
High-temperature calcination removes double-template (surfactant and polyurethane sponge) after material ageing, abundant drying, most end form
At with silicon and calcium, phosphorus multilevel structure as main component (micron macropore, mesoporous nano) timbering material.
The performance of the silicon substrate bone renovating bracket material of micron-nanometer multi pore structure
The silicon substrate bone renovating bracket material with micron-nanometer multi pore structure that the present invention prepares, mechanical property
It can show themselves in that the mechanical property of compound rest is directly proportional to enhancing agent content, its mechanical strength reaches as high as when high porosity
10MPa。
The silicon substrate bone renovating bracket material with micron-nanometer multi pore structure that the present invention prepares, multi-stage porous
Structure shows themselves in that micron order macropore: 200-500 μm；Adjustable nanoscale is mesoporous: 2-22nm.
The silicon substrate bone renovating bracket material with micron-nanometer multi pore structure that the present invention prepares, connection are big
Hole porosity 50-95% is controllable；Its specific surface area is high simultaneously, can reach 150-600m2/g。
The purposes of the silicon substrate bone renovating bracket material of micron-nanometer multi pore structure
The silicon substrate bone renovating bracket material with micron-nanometer multi pore structure that the present invention obtains has good life
Activity and cellular response, and be conducive to the exchange circulation of nutriment and metabolic products, it is provided for blood vessel, growing into for tissue
Sufficient space.With good Bioactivity and cell compatibility.
The silicon substrate bone renovating bracket material with micron-nanometer multi pore structure that the present invention obtains, can be used as albumen, medicine
The slow-releasing system of object and growth factor.The high activity that growth factor can be achieved loads and controlled release；The three-dimensional structure benefit of bracket simultaneously
In the adherency, migration and infiltration of cell.
The silicon substrate bone renovating bracket material with micron-nanometer multi pore structure that the present invention obtains, have it is good can
Plasticity and mechanical strength, inorganic strengthening agent have the function of significantly improving compound rest mechanical strength, improves its compression strength
It is 100 times of silicon substrate bracket or more of the polyurethane foam plank method preparation of other relevant reports to 10MPa or more
(Micropor.Mesopor.Mater,2011;143:311–319)。
Compared with traditional ceramic-like porous support, compound bone repairing support prepared by the present invention has superior mechanics
Performance and controllable multilevel structure and suitable degradation rate, can not only provide support, and keep certain time straight for cambium
There is own biological mechanical characteristic to cambium；And be connected to macroscopical macropore can for nutrition transmission, angiogenic growth, cell migration and
Tissue, which is grown into, provides space, the growth of sertoli cell and the expression of function, while nanoscale is mesoporous can be effectively controlled drug, albumen
With the release of growth factor, promote the proliferation and directed differentiation of cell.Silicon substrate high intensity multilevel structure Bone Defect Repari branch of the invention
Frame may be used as bone tissue engineering scaffold and slow releasing carrier of medication etc..
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.
Evaluation method
(1) characterization of material
The macroscopic view knot of material is prepared using scanning electron microscopy Electronic Speculum (SEM, JSM-6360LV, JEOL, Japan) observation
Structure, deposition mineralising and cell are sprawled.Using Jie of transmission electron microscope (HRTEM, JEM-2100, Japan) observation material
Pore structure.It is counted using the microcellular structure of isothermal nitrogen adsorption-desorption (Micromeritics, USA) measurement material, and by BET
The specific surface area and Kong Rong for calculating material calculate average pore size according to Barrett-Joyner-Helen (BJH) formula.Using laser
It is copolymerized the cell morphology and infiltration of burnt (CLSM, Leica Microsystems, Heidelberg, Germany) observation material surface
Thoroughly.Using New born formation situation at x-ray instrument detection bone defect.
(2) Measurement of Material Mechanical Performance
10mm × 10mm × 10mm rectangle galley proof is made in bracket, then on universal testing machine (AG-2000A,
Shimadzu, Japan) carry out compression test, compression speed 1mm/min.
(3) Cell culture invitro
Mouse mesenchymal stem cell (rBMSCs) is incubated at containing 10% fetal calf serum, 100U/mL penicillin, 100U/mL chain
In the α-MEM culture solution of mycin, in 37 DEG C, 5%CO2Secondary culture in incubator.Macropore bracket high-temperature sterilization is placed on 24 holes
In tissue culture plate, rBMSCs is inoculated into material surface respectively, and culture medium is added；It is measured after being incubated for culture using MTT
Method detects cell activity and cell Proliferation, and the tetramethyl azo azoles salt reagent of 100 μ L is added to every hole, and 37 DEG C are continued to be incubated for 4h
Afterwards, it inhales and abandons supernatant, 1mL DMSO is added, gently shakes 20min, dissolves crystal, existed using continuous spectrum microplate reader
The absorbance value of solution is measured at 490nm.
Observe cell morphology by SEM: by cell inoculation, three times, 2.5% glutaraldehyde is fixed for PBS cleaning after 6h on material
Ethyl alcohol is dehydrated step by step after 15min: 50%, 70%, 80%, 90%, 95%, 100%, each 5min；With isoamyl acetate displacement 10min；
Culture after treatment is had the material of cell to observe under scanning electron microscope by 37 DEG C of metal sprayings after oven drying 4 hours again.
Cell is observed in 8 He of embodiment by laser co-focusing (confocal laser scanning microscopy)
It infiltration on 13 bracket and sprawls: by 2*104The cell culture in a/hole on material for 24 hours after PBS cleaning three times, 2.5% penta
It is dyed 40 minutes after the fixed 15min of dialdehyde with the phalloidine (FITC-Phalloidin) of marked by fluorescein isothiocyanate, PBS
5 times, each 5min are cleaned, then cleans 5 times, each 5min with PBS after DAPI dyeing 10min, laser is copolymerized after mounting fluid-tight piece
Coke is lower to carry out three dimensional viewing.
(4) in vivo at Bone Defect Repari
The animal model of use is the critical defect of rabbit radius middle section 15mm.By silicon substrate high intensity multi-stage micro-nano structure composite support
It is 1.5cm, diameter 4mm, then radiation sterilization that length, which is made, in frame.It tests and is carried out in sterile operating room.Preoperative 3% (w/w) penta
Barbital sodium is injected intravenously anesthetized animal by 30mg/kg, takes the stringer notch of about 30mm in right fore radius middle section, successively separates
Soft tissue appears radius, causes 15mm defect with dental burr in radius middle section, immediately with inserting material after normal saline flushing, then
Layer-by-layer tight sewing-up cut.Postoperative different time points take out the ulna of defect radius and its connection, and X-ray detects at bone defect
New born formation situation.
The preparation of embodiment 1, mesoporous silicon microballoon reinforcing agent 1
It weighs 4.8g P123 and 120mL H is added2In the concentrated hydrochloric acid (12mol/L) of O and 20mL.It is vigorously stirred living to surface
Property agent (P123) be completely dissolved to after transparent, 3.75g four water-calcium nitrate, 0.62g triethyl phosphate and the positive silicic acid second of 7.42g is added
Ester.It is stirred for 24 hours at 35 DEG C.Obtain mesoporous silicon microballoon reinforcing agent 1.
If prepared material dries, is sintered the average mesopore aperture that can measure powder are as follows: 3.5nm, BET calculation result table
The specific surface area of bright material is 829m2/g。
The preparation of embodiment 2, mesoporous silicon microballoon reinforcing agent 2
It weighs 4.8g P123 and 120mL H is added2In the concentrated hydrochloric acid (12mol/L) of O and 20mL.It is vigorously stirred living to surface
Property agent (P123) be completely dissolved after, 3.75g four water-calcium nitrate, 0.62g triethyl phosphate and 7.42g ethyl orthosilicate is added.35
Stirred at DEG C for 24 hours after 100 DEG C of hydro-thermal process for 24 hours.Obtain mesoporous silicon microballoon reinforcing agent 2.
If prepared material dries, is sintered the average mesopore aperture that can measure powder are as follows: 8.2nm, BET calculation result table
The specific surface area of bright material is 781m2/g。
The preparation of the non-mesoporous silicon substrate microballoon 3 of embodiment 3
It measures 50mL ethyl alcohol and adjusts pH to 2 hereinafter, 0.76g four water-calcium nitrate, 0.23g triethyl phosphate and 5.2g is added just
Silester.35 DEG C stirring for 24 hours afterwards ageing and ball milling for 24 hours.If BET calculated result shows after prepared material is dried, is sintered
The specific surface area of material is 46m2/g。
The preparation of embodiment 4, mesoporous silicon based xerogel material 1
It weighs 4g F127 and 50mL ethyl alcohol and 1g concentration is added as in the hydrochloric acid of 0.5M.It is complete to surfactant (F127)
Be dissolved to it is transparent after, 0.76g four water-calcium nitrate, 0.23g triethyl phosphate and 5.2g ethyl orthosilicate is added.It is stirred at 40 DEG C
Being aged afterwards for 24 hours to viscosity is 5 × 104MPa obtains mesoporous silicon based xerogel material 1.
If prepared material can measure average mesopore aperture after drying, be sintered, milling are as follows: 7.2nm, BET calculated result
The specific surface area for showing material is 352.5m2/g。
The preparation of embodiment 5, mesoporous silicon based xerogel material 2
It weighs 4g P123 and 50mL ethyl alcohol and 1g concentration is added as in the hydrochloric acid of 0.5M.It is complete to surfactant (P123)
After dissolution, 0.96g four water-calcium nitrate, 0.28g triethyl phosphate and 6.70g ethyl orthosilicate is added.30 DEG C of stirrings are aged afterwards for 24 hours
It is 5 × 10 to viscosity4MPa.Obtain mesoporous silicon based xerogel material 2.
If prepared material can measure average mesopore aperture after drying, be sintered, milling are as follows: 4.3nm, BET calculated result
The specific surface area for showing material is 312.7m2/g。
Preparation--7MBG of embodiment 6, silicon substrate multi-stage micro-nano structure timbering material
By the preparation of embodiment 4 aperture be 7.2nm, viscosity is 5 × 104The mesoporous silicon based xerogel material 1 of MPa respectively with
0.7g/1cm3(timbering material that can get porosity ≈ 65%), 0.6g/1cm3(timbering material that can get porosity ≈ 75%),
0.5g/1cm3(quality refers to mesoporous silicon based xerogel material matter to the mass volume ratio of (timbering material that can get porosity ≈ 85%)
Amount, volume refer to sponge volume, rear same) (polyurethane sponge uses matter on being cast in the polyurethane sponge for cutting size in advance
Deionized water is rinsed and is dried after the NaOH that amount score is 20% pre-processes 20min, rear same), room temperature ageing and 60 DEG C of drying 48h,
600 DEG C of calcining 6h obtain required timbering material.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 7.2nm, BET calculated result show that the specific surface area of material is 352.5m2/g。
Preparation--7MBG-5MP of embodiment 7, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
Mesoporous silicon microballoon reinforcing agent 2 prepared by embodiment 2 is uniformly mixed embodiment 4 to make by way of physical doping
Standby aperture is 7.2nm, viscosity is 5 × 104The mesoporous silicon based xerogel material 1 of MPa, mesoporous silicon based xerogel material 1: mesoporous
The mass ratio of silicon microballoon reinforcing agent 2 is 100:5.By resulting complex sol respectively with 0.7g/1cm3(it can get porosity ≈
65% timbering material), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get porosity
The timbering material of ≈ 85%) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing and 60
DEG C drying 48h, 600 DEG C of calcining 6h obtain timbering material 7MBG-5MP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 7.5nm, BET calculated result show that the specific surface area of material is 389.5m2/g。
Preparation--7MBG-10MP of embodiment 8, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
Mesoporous silicon microballoon reinforcing agent 2 prepared by embodiment 2 is uniformly mixed embodiment 4 to make by way of physical doping
The viscosity that standby aperture is 7.2nm is 5 × 104The mesoporous silicon based xerogel material 1 of MPa, mesoporous silicon based xerogel material 1: mesoporous
2 mass ratio of silicon microballoon reinforcing agent is 100:10.By resulting complex sol respectively with 0.7g/1cm3(it can get porosity ≈ 65%
Timbering material), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get porosity ≈ 85%
Timbering material) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing and 60 DEG C baking
Dry 48h, 600 DEG C of calcining 6h obtain timbering material 7MBG-10MP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 7.4nm, BET calculated result show that the specific surface area of material is 402.4m2/g。
Preparation--7MBG-20MP of embodiment 9, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
Mesoporous silicon microballoon reinforcing agent 2 prepared by embodiment 2 is uniformly mixed embodiment 4 to make by way of physical doping
The viscosity that standby aperture is 7.2nm is 5 × 104The mesoporous silicon based xerogel material 1 of MPa, mesoporous silicon based xerogel material 1: mesoporous
2 mass ratio of silicon microballoon reinforcing agent is 100:20.By resulting complex sol respectively with 0.7g/1cm3(it can get porosity ≈ 65%
Timbering material), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get porosity ≈ 85%
Timbering material) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing and 60 DEG C baking
Dry 48h, 600 DEG C of calcining 6h obtain timbering material 7MBG-20MP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 7.4nm, BET calculated result show that the specific surface area of material is 425.4m2/g。
Preparation--7MBG-40MP of embodiment 10, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
Mesoporous silicon microballoon reinforcing agent 2 prepared by embodiment 2 is uniformly mixed embodiment 4 to make by way of physical doping
The viscosity that standby aperture is 7.2nm is 5 × 104The mesoporous silicon based xerogel material 1 of MPa, mesoporous silicon based xerogel material 1: mesoporous
2 mass ratio of silicon microballoon reinforcing agent is 100:40.By resulting complex sol respectively with 0.7g/1cm3(it can get porosity ≈ 65%
Timbering material), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get porosity ≈ 85%
Timbering material) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing and 60 DEG C baking
Dry 48h, 600 DEG C of calcining 6h obtain timbering material 7MBG-40MP.
Preparation--4MBG of embodiment 11, silicon substrate multi-stage micro-nano structure timbering material
It is 5 × 10 by the viscosity that the preparation of embodiment 5 aperture is 4.3nm4The mesoporous silicon based xerogel material 2 and poly- ammonia of MPa
Ester sponge is respectively with 0.7g/1cm3(timbering material that can get porosity ≈ 65%), 0.6g/1cm3(it can get porosity ≈ 75%
Timbering material), 0.5g/1cm3The mass volume ratio of (timbering material that can get porosity ≈ 85%) is being cast in preparatory sanction
It shears on the polyurethane sponge of size, simultaneously 60 DEG C of drying 48h, 600 DEG C of calcining 6h obtain required timbering material for room temperature ageing.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 4.3nm, BET calculated result show that the specific surface area of material is 312.7m2/g。
Preparation--4MBG-5MP of embodiment 12, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
The mesoporous silicon microballoon reinforcing agent 1 that embodiment 1 prepares uniformly is mixed into implementation by way of physical doping
The viscosity that aperture prepared by example 5 is 4.3nm is 5 × 104The mesoporous silicon based xerogel material 2 of MPa, mesoporous silicon based xerogel material
2: 1 mass ratio of mesoporous silicon microballoon reinforcing agent is 100:5.By resulting complex sol respectively with 0.7g/1cm3(it can get porosity
The timbering material of ≈ 65%), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get porosity
The timbering material of ≈ 85%) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing and 60
DEG C drying 48h, 600 DEG C of calcining 6h obtain required timbering material 4MBG-5MP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 4.2nm, BET calculated result show that the specific surface area of material is 315.8m2/g。
Preparation--4MBG-10MP of embodiment 13, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
The mesoporous silicon microballoon reinforcing agent 1 that embodiment 1 prepares uniformly is mixed into implementation by way of physical doping
The viscosity that aperture prepared by example 5 is 4.3nm is 5 × 104The mesoporous silicon based xerogel material 2 of MPa, mesoporous silicon based xerogel material
2: 1 mass ratio of mesoporous silicon microballoon reinforcing agent is 100:10.By resulting complex sol respectively with 0.7g/1cm3(it can get hole
The timbering material of rate ≈ 65%), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get hole
The timbering material of gap rate ≈ 85%) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing
And 60 DEG C of drying 48h, 600 DEG C of calcining 6h obtain required timbering material 4MBG-10MP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 4.2nm, BET calculated result show that the specific surface area of material is 346.3m2/g。
Preparation--4MBG-20MP of embodiment 14, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
The mesoporous silicon microballoon reinforcing agent 1 that embodiment 1 prepares uniformly is mixed into implementation by way of physical doping
The viscosity that the preparation preparation of example 5 aperture is 4.3nm is 5 × 104The mesoporous silicon based xerogel material 2 of MPa, mesoporous silicon based xerogel material
Material 2: 1 mass ratio of mesoporous silicon microballoon reinforcing agent is 100:20.By resulting complex sol respectively with 0.7g/1cm3(it can get hole
The timbering material of gap rate ≈ 65%), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get hole
The timbering material of gap rate ≈ 85%) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing
And 60 DEG C of drying 48h, 600 DEG C of calcining 6h obtain required timbering material 4MBG-20MP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 4.2nm, BET calculated result show that the specific surface area of material is 362.8m2/g。
Preparation--4MBG-10NMP of embodiment 15, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
The non-mesoporous silicon microballoon reinforcing agent 3 that embodiment 3 is prepared uniformly mixes reality by way of physical doping
Applying example 5 and preparing the viscosity that aperture is 4.3nm is 5 × 104The mesoporous silicon based xerogel material 2 of MPa, mesoporous silicon based xerogel material
2: non-1 mass ratio of mesoporous silicon microballoon reinforcing agent is 100:10.By resulting complex sol respectively with 0.7g/1cm3(it can get hole
The timbering material of gap rate ≈ 65%), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get hole
The timbering material of gap rate ≈ 85%) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing
And 60 DEG C of drying 48h, 600 DEG C of calcining 6h obtain required timbering material 4MBG-10NMP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 4.2nm, BET calculated result show that the specific surface area of material is 206.5m2/g。
Preparation--7MBG-10NMP of embodiment 16, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
Non- mesoporous silicon microballoon reinforcing agent 3 prepared by embodiment 3 uniformly mixes embodiment by way of physical doping
The viscosity that 4 preparation apertures are 7.2nm is 5 × 104The mesoporous silicon based xerogel material 1 of MPa, mesoporous silicon based xerogel material 1: non-
2 mass ratio of mesoporous silicon microballoon reinforcing agent is 100:10.By resulting complex sol respectively with 0.7g/1cm3(it can get porosity
The timbering material of ≈ 65%), 0.6g/1cm3(timbering material that can get porosity ≈ 75%), 0.5g/1cm3(it can get porosity
The timbering material of ≈ 85%) mass volume ratio be cast in advance cut size polyurethane sponge on, room temperature ageing and 60
DEG C drying 48h, 600 DEG C of calcining 6h obtain timbering material 7MBG-10NMP.
According to 0.6g/1cm3It is poured the timbering material obtained, if prepared timbering material can measure average Jie after milling
Hole aperture are as follows: 7.4nm, BET calculated result show that the specific surface area of material is 221.4m2/g。
Embodiment 17, silicon substrate high intensity multi-stage micro-nano structure compound support frame material mechanical property
Photo such as Fig. 1 of the high-intensitive multilevel structure compound support frame material of embodiment 6-9.The high intensity of embodiment 8,13 is more
The SEM figure such as Fig. 2 of level structure compound support frame material.The TEM of the high-intensitive multilevel structure compound support frame material of embodiment 8,13 schemes
Such as Fig. 3.As it can be seen that having 200-500 μm of micron order macropore and 2-22nm mesoporous nano in the timbering material.
Silicon substrate high intensity multi-stage micro-nano structure compound support frame material is prepared into 10mm × 10mm × 10mm rectangle batten, so
(AG-2000A, Shimadzu, Japan) carries out compression test, compression speed 1mm/min on universal testing machine afterwards.
By taking embodiment 6-16 as an example, as a result as shown in Table 3 and Table 4.The introducing of inorganic strengthening agent can improve porous branch extremely significantly
The mechanical strength of frame material.
The porosity of porous support materials is measured according to drainage, porosity P=(W2-W3+WS)/(W1-W3), wherein WSFor
Sample quality, W1For the quality for weighing the specific gravity bottle full of dehydrated alcohol；W2For sample to be put into the gross mass in specific gravity bottle；W3
After sample is taken out, the quality of specific gravity bottle.)
Table 3, embodiment 6-10,16 compound support frame material compression strength
Table 4, embodiment 11-15 compound support frame material compression strength
The Bioactivity of embodiment 18, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
Silicon substrate high intensity multi-stage micro-nano structure compound support frame material is immersed in human body simulation body fluid (using electronic analysis day
It is flat to accurately weigh reagent and in strict accordance with following sequence and dosage: 7.996g NaCl, 0.353gNaHCO3,0.224g KCl,
0.228g K2HPO43H2O,0.305g MgCl26H2O,0.045g HCl,0.278g CaCl20.071g Na2SO4,6.057g
CNH2(CH2OH)3) in, since a series of physical-chemical reaction can occur rapidly for the surface of mesoporous silicon based xerogel material, lead
Cause its surface formed one layer of carbonate hydroxyapatite (HAP) similar with skeleton inorganic phase, so as to human body firmly, soft tissue
If collagen and cell are further at key joint.By taking the timbering material that the present embodiment 8 and embodiment 16 obtain as an example, pass through
SEM can deposition with phenetic analysis HAP on the timbering material surface of embodiment 8, such as Fig. 4.It can be found that with non-mesoporous silicon
The 7MBG-10NMP of base microballoon enhancing is compared, and has more excellent external mineralising energy using 7MBG-10MP prepared by the present invention
Power and bioactivity.
The cell compatibility of embodiment 19, silicon substrate high intensity multi-stage micro-nano structure compound support frame material
With mouse mesenchymal stem cell (rBMSCs), (1, rat 100g or so take off neck and put to death, and 75% alcohol steeps 10min.
2, sterile removing femur, shin bone, then the muscle on bone to the greatest extent is shelled with gauze.3, metaphysis is cut, is contained with the absorption of 5ml syringe
10% fetal calf serum (does not inactivate) L-DMEM culture medium and rinses ossis, blows and beats the single cell suspension of system.4, be centrifuged 1000r/min,
It is centrifuged 5min.5, supernatant is abandoned, cell is resuspended in culture medium, blows and beats into cell suspension, is seeded in culture bottle and cultivates.) it is model, make
With the cell activity of mtt assay detection embodiment 6-9, the timbering material of embodiment 11-14 preparation: to being inoculated with cell (2*104
A/hole) timbering material be incubated in 24 orifice plates, the tetramethyl azo azoles salt reagent of 100 μ L is added in every hole, and 37 DEG C are continued to incubate
It after educating 4h, inhales and abandons supernatant, 1mL DMSO is added, gently shakes 20min, dissolves crystal, continuous spectrum is used after centrifugation
Microplate reader measures the absorbance value of solution at 490nm.Cell activity and cell Proliferation such as Fig. 5 that mtt assay measures, it is seen that with
The increase of time, cell activity is good, has good biocompatibility.
Cell is observed in the pattern on the timbering material surface of embodiment 8 and 13 by scanning electron microscope sem: by 2*104A/hole
70% three times, ethyl alcohol is dehydrated cell inoculation step by step after the fixed 15min of 2.5% glutaraldehyde for PBS cleaning after 12h on material: 50%,
80%, 90%, 95%, 100%, each 5min；With isoamyl acetate displacement 10min；37 DEG C of metal sprayings after oven drying 4 hours again will be through
Crossing treated, culture has the material of cell to be observed under scanning electron microscope.As a result such as Fig. 6, it is seen that cell is in timbering material table
Face, which has, to adhere to and sprawls well.
Cell is observed in 8 He of embodiment by laser co-focusing (confocal laser scanning microscopy)
It infiltration on 13 timbering material and sprawls: by 2*104Rear PBS is cleaned three times for 24 hours on material for the cell culture in a/hole,
40 points are dyed with the phalloidine (FITC-Phalloidin) of marked by fluorescein isothiocyanate after the fixed 15min of 2.5% glutaraldehyde
Clock, PBS cleans 5 times, each 5min, then cleans 5 times, each 5min with PBS after DAPI dyeing 10min, swashs after mounting fluid-tight piece
The burnt lower progress three dimensional viewing of light copolymerization.As a result such as Fig. 7, it is seen that porous support materials are conducive to the infiltration of cell and grow into, and table
Reveal good cell adherence and compatibility.
Analysis in embodiment 20, silicon substrate high intensity multi-stage micro-nano structure compound support frame material implantation animal body
Observe Bone Defect Repari effect of the timbering material after implanting by X-ray: the animal model that this research uses is rabbit
The critical defect of radius middle section 15mm.7MBG-10MP silicon substrate high intensity multi-stage micro-nano structure compound rest material prepared by embodiment 8
It is 1.5cm, diameter 4mm, then radiation sterilization that length, which is made, in material.It tests and is carried out in sterile operating room.Preoperative 3% (w/w) penta
Barbital sodium is injected intravenously anesthetized animal by 30mg/kg, takes the stringer notch of about 30mm in right fore radius middle section, successively separates
Soft tissue appears radius, causes 15mm defect with dental burr in radius middle section, immediately with inserting material after normal saline flushing, then
Layer-by-layer tight sewing-up cut.The ulna of defect radius and its connection is taken out within postoperative 2 weeks and 12 weeks, X-ray detects new at bone defect
Ostosis situation.As a result such as Fig. 8, it is seen that prepared silicon substrate high intensity multi-stage micro-nano structure compound support frame material improves silicon substrate
Low, easily scaling-off, molding the is difficult disadvantage of porous support mechanical strength, and preferable skeletonization effect is presented in vivo.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of silicon substrate bone renovating bracket material with micron-nanometer multi pore structure, have in the timbering material
200-500 μm of micron order macropore and 2-22nm mesoporous nano, the timbering material include:
100 parts by weight of mesoporous silicon based xerogel material；With
Mesoporous silicon oxide microballoons 5-40 parts by weight.
2. silicon substrate bone renovating bracket material as described in claim 1, which is characterized in that the timbering material is prepared as follows:
(1) 100 parts by weight of mesoporous silicon based xerogel material and mesoporous silicon oxide microballoons 5-40 parts by weight are mixed；
(2) by the mixture of (1) with 0.3-0.8g/1cm3Mass volume ratio be cast on polyurethane sponge, be aged, dry, forge
It burns, obtain the timbering material.
3. silicon substrate bone renovating bracket material as described in claim 1, which is characterized in that the mesoporous silicon oxide microballoons packet
It includes: MCM-41, SBA-15, bio-vitric microballoon.
4. silicon substrate bone renovating bracket material as claimed in claim 2, which is characterized in that the mesoporous silicon oxide microballoons are as follows
Preparation: surfactant 1-10 parts by weight are added in aqueous solvent, salt acid for adjusting pH is abundant to surfactant less than 2
It is dissolved to transparent rear addition four water-calcium nitrate 0.5-10 parts by weight, triethyl phosphate 0.1-10 parts by weight, ethyl orthosilicate 3-50
Parts by weight；24 ± 1h is stirred at 35 ± 5 DEG C.
5. silicon substrate bone renovating bracket material as claimed in claim 2, which is characterized in that the mesoporous silicon based xerogel material
Following preparation: surfactant 1-15 parts by weight are added in aqueous solvent, salt acid for adjusting pH is filled less than 2 to surfactant
Divide and is dissolved to transparent rear addition four water-calcium nitrate 0.3-5 parts by weight, triethyl phosphate 0.1-4 parts by weight and ethyl orthosilicate 3-50
Parts by weight；Ageing to viscosity is (4-7) × 10 after stirring 24 ± 1h at 35 ± 5 DEG C4MPa。
6. the silicon substrate bone renovating bracket material as described in claim 4-5 is any, which is characterized in that the surfactant choosing
From: cetyl trimethylammonium bromide, P123, F127.
7. the preparation method of silicon substrate bone renovating bracket material described in claim 1, which is characterized in that the described method includes:
(1) 100 parts by weight of mesoporous silicon based xerogel material and mesoporous silicon oxide microballoons 5-40 parts by weight are mixed；
(2) by the mixture of (1) with 0.3-0.8g/1cm3Mass volume ratio be cast on polyurethane sponge, be aged, dry, forge
It burns, obtain the timbering material.
8. silicon substrate bone renovating bracket material as claimed in claim 7, which is characterized in that the silicon substrate bone renovating bracket material
Following preparation: it is mesoporous that 5-40 parts by weight mesoporous inorganic microballoon is uniformly dispersed in 100 parts by weight by way of physical doping
In silicon based xerogel material, by resulting complex sol with 0.3-0.8g/1cm3Mass volume ratio be cast in polyurethane sea
On silk floss, simultaneously 60 ± 5 DEG C of drying 48 ± 6h, 600 ± 100 DEG C of 6 ± 2h of calcining obtain the timbering material for room temperature ageing.
9. the purposes of silicon substrate bone renovating bracket material described in claim 1, which is characterized in that
It is used to prepare bone tissue engineering scaffold；
Be used to prepare drug, albumen, growth factor controlled release carrier；Or
It is used to prepare cell culturing bracket.
10. the purposes of mesoporous silicon oxide microballoons, which is characterized in that mix mesoporous silicon oxide microballoons and mesoporous silicon based xerogel material
It closes, is used to prepare the silicon substrate bone renovating bracket material with micron-nanometer multi pore structure；The mesoporous silicon oxide microballoons packet
It includes: MCM-41, SBA-15, bio-vitric microballoon；The mesoporous silicon oxide microballoons are prepared as follows: by surfactant 1-10 weight
Amount part be added in aqueous solvent, salt acid for adjusting pH less than 2, after surfactant be sufficiently dissolved to it is transparent after four water nitric acid are added
Calcium 0.5-10 parts by weight, triethyl phosphate 0.1-10 parts by weight, ethyl orthosilicate 3-50 parts by weight；At 35 ± 5 DEG C stirring 24 ±
1h。
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| CN106701569A (en) | 2015-08-18 | 2017-05-24 | 重庆润泽医药有限公司 | Tissue cell culture device |
| CN106606805B (en) * | 2015-10-22 | 2020-05-19 | 中国科学院上海硅酸盐研究所 | Nano-bioglass coated patterned electrospun fibrous membrane and preparation method and application thereof |
| TWI659939B (en) | 2017-06-23 | 2019-05-21 | 高雄醫學大學 | Ceramic material having a positive slowly release effect, method for manufacturing the same, and system comprising the same |
| CN108992706A (en) * | 2018-08-08 | 2018-12-14 | 上海应用技术大学 | A kind of antibiotic continues acrylic resin bone cement efficiently discharged and preparation method thereof |
| CN109276763A (en) * | 2018-09-29 | 2019-01-29 | 深圳先进技术研究院 | Polyose modification MBG bracket, tissue recovery support and its preparation method and application |
| CN112675830B (en) * | 2021-01-12 | 2022-04-22 | 万华化学集团股份有限公司 | Aldol condensation catalyst, preparation method and method for preparing methyl methacrylate by using aldol condensation catalyst |
| CN112933297A (en) * | 2021-03-01 | 2021-06-11 | 上海交通大学医学院附属第九人民医院 | Multistage micro-nano structure bone repair scaffold for freeze-drying delivery of exosomes |
| CN115920133A (en) * | 2022-09-14 | 2023-04-07 | 上海交通大学医学院附属第九人民医院 | Porous combined bracket for bone repair and medical instrument thereof |
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