CN107308499A - Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application - Google Patents
Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract
The present invention relates to Material Field, a kind of nanometer biological glass/polymer three-dimensional porous material is disclosed, using bioactive polymer as packing material, the porous microsphere shape nanometer biological glass of rare earth doped element is support；Its large aperture is 5~500 μm, porosity 40%~90%.Preparation method comprises the following steps：(1) take the porous microsphere shape nano grade biological glass biology of rare earth doped element uniformly to be mixed with living polymer solution, obtain mixed slurry；(2) mixed slurry freeze-drying shaping, is made nanometer biological glass/polymer three-dimensional composite porous.The inventive method is simple, easy to operate, environmentally friendly, and microspheroidal nano grade biological glass/polymer three-dimensional porous material of the rare earth doped element of synthesis has good biocompatibility and osteanagenesis, is had a good application prospect in bone renovating material field.
Description
Technical field
The present invention relates to Material Field, technical field of biological material, field of inorganic nonmetallic material, inorganic metallic materials field and
Organic material field, the microspheroidal nano grade biological glass three-dimensional of specially a kind of rare earth doped element it is composite porous and
Its preparation method.
Technical background
Serious bone wound or bone tumour resection is postoperative often to leave either large or small Cranial defect, and clinician needs should
It is filled up with various bone renovating materials, repaired.Although autologous bone transplanting is always repairing bone defect " goldstandard ", its
In the presence of increase wound, bone amount it is limited, for area's complication the shortcomings of, and allogenic bone transplantation is also because may spread disease, exempt from
Epidemic disease rejection and have impact on extensive use.Since preparing bio-vitric from nineteen sixty, bio-vitric is by itself good
Biocompatibility and biological degradability and for the good power of regeneration of defective bone, in past more than 40 years, bio-vitric draws
The interest of numerous researchers is played.Fusion method bio-vitric is first generation bio-vitric, and its product is in plastic surgery and tooth
Applied well during section etc. is clinical, have been achieved for good therapeutic effect.But fusion method itself is not allowed in the presence of some
The shortcoming of ignorance, such as high-temperature fusion process energy consumption is larger, and grinding sieving further results in objectionable impurities doping and causes particle
The phenomenon such as pattern is irregular, granularity is uneven.
In order to solve traditional biological activity glass structure, the problems such as form is uncontrollable, templating self-assembly technology combination colloidal sol
It is a kind of new method for preparing bio-vitric that gel, which prepares bio-vitric,.Sol-gel bioglass is the new doctor of a class
With bioactive materials, it can be used for preparing bone renovating material and bone tissue engineering scaffold.Collosol and gel hair bio-vitric is broken through
Tradition prepares the shortcoming of bio-vitric, can make SiO in bio-vitric2Improved in bio-vitric constituent content to 90%, this
Also bio-vitric is promoted to have wider array of application.The bio-vitric prepared compared to fusion method, life prepared by sol-gal process
Thing glass has nanostructured, so that bio-vitric has the bioactivity of bigger specific surface area and Geng Gao.But at present
Most researcher, when preparing bio-vitric, mainly prepares biological glass in acid condition using sol-gal process
Glass.Prepared compared to acid condition under bio-vitric, alkalescence condition, sol-gel bioglass can be very good to control biological glass
The pattern of glass.But, the nano level bio-vitric powder of preparation is difficult to directly apply to Bone Defect Repari conveniently, how to fix biology
Glass powder, allows bio-vitric powder carrying out Bone Defect Repari, the problem of be also one relatively difficult.
Chinese patent application 105541086A, discloses a kind of method for preparing Porous bioglass support, is prepared for one
Plant porosity height, the bio-vitric stent Methods that connectivity is good, aperture is controllable.
Chinese patent application CN106267374A, discloses a kind of 3 D-printing mesoporous biological containing the strontium glass of biological absorbable
There is provided 3 D-printing mesoporous bioglass containing strontium support of a kind of biological absorbable and preparation method thereof, the biology for glass support
Absorbable 3 D-printing mesoporous bioglass containing strontium support can be applied to the reparation and treatment for Cranial defect, with good
Biocompatibility, have preferably promote skeletonization ability and can by living organism absorb degrade.
When current most of researchers prepare bio-vitric, mainly life is improved by adulterating a small amount of trace element
The bioactivity of thing glass.For example, the trace element such as Sr, Zn, Mg and Si that adulterated in bio-vitric, their increasings to cell
Grow, bone mineralising and improve bone strength etc. and play an important role.Although rare earth ion is not a kind of life essential metal element,
But recently as extensive application of the rare earth in terms of industrial or agricultural, medicine, rare earth more and more causes numerous researchs
The extensive concern of person.Many documents are reported that rare earth ion has the effect of " low to promote high suppression ", i.e. rare earth ion for cell
At low concentrations, cash as the facilitation to normal cell, rare earth ion in higher concentrations, is cashed as one to normal cell
Straight effect.
The common preparation method of current porous support materials has addition pore creating material method, foaming, has foam impregnation method etc.,
The microspheroidal nano grade biological glass three-dimensional that the present invention prepares a kind of rare earth doped element using freeze-drying is porous compound
Material, this preparation method is simple, it is easy to operate, and the three-dimensional porous composite prepared, and porosity is high, and connectivity is good.
Based on this, the present invention prepares a kind of microspheroidal nano grade biological glass of rare earth doped element using freeze-drying
Composite porous, this material has the higher biofacies same sex, available for for bone defect healing, in terms of osteogenic ability
Play the role of outstanding, be expected to the ideal stent material as Bone Defect Repari.
The content of the invention
It is an object of the invention to provide the microspheroidal nano grade biological glass of a kind of rare earth doped element/high-molecular porous multiple
Condensation material, the material has higher voidage, and connectivity is good, available for Bone Defect Repari.
It is a further object to provide microspheroidal nano grade biological glass/macromolecule of above-mentioned rare earth doped element
Composite porous preparation method, the preparation technology is not only simple but also short preparation period, and production cost is low.
Above-mentioned thing bio-vitric timbering material is applied to Bone Defect Repari field by the present invention.
The technical scheme is that：A kind of nanometer biological glass/polymer three-dimensional porous material, with three-dimensional porous knot
Structure, its large aperture is 5~500 μm, porosity 40%~90%；Using bioactive polymer as support, with rare earth doped element
Porous microsphere shape nanometer biological glass be packing material.
It is preferred that, it is used as the porous microsphere shape nanometer biological glass mean surface pore size of the rare earth doped element of packing material
For 2~3.5nm, specific surface area is 200~300m2/g；Particle diameter is 100~400nm, preferably 200~350nm；Consisting of
xSiO2yP2O5wRe2O3zCaO；
Wherein Re is thulium, selected from thuliums such as ytterbium, gadolinium, cerium or lanthanums；W, x, y, z are Mole percent
Number, 0<X≤80%, 0<Y≤10%, 0<Z≤36%, 0<W≤18%, w+x+y+z=1.It is preferred that, (x+y)/(w+z)=3~
8:1；X/y=10~25:1, z/w=2~10：1.In a preferred embodiment of the present invention, (x+y)/(w+z)=5.25, x/y=
20, z/w=3~7：1.
The porous microsphere shape nanometer biological glass of rare earth doped element and the mass ratio of bioactive polymer are 1：0.1~
10, preferably 1：0.3~5, more preferably 1：0.5~3.
Described bioactive polymer is chitosan, collagen, polyvinylpyrrolidone, poly butyric ester, poly-
Caprolactone or any mixture.
The material mainly includes high polymer material, rare earth mixing with nano bio-vitric, possesses the macropore knot of three-dimensional insertion
Structure, its aperture is 5~500 μm, and porosity is 40~90%, with good biocompatibility and biological degradability, is also had
The performance of excellent promotion osteanagenesis；The structural formula of above-mentioned rear-earth-doped bio-vitric is xSiO2yP2O5wRe2O3zCaO。
The above-mentioned rare earth mixing with nano bio-vitric/composite porous preparation method of chitosan three-dimensional, its specific step
Suddenly include：
(1) the porous microsphere shape nano grade biological glass biology of rare earth doped element is taken uniformly to be mixed with living polymer solution
Close, obtain mixed slurry；
(2) mixed slurry freeze-drying shaping, is made nanometer biological glass/polymer three-dimensional composite porous.
In step (1), the porous microsphere shape nanometer biological glass and the quality of bioactive polymer of rare earth doped element
Than for 1：0.1~10, preferably 1：0.3~5, more preferably 1：0.5~3.Rear-earth-doped bio-vitric and bioactivity high score
The amount ratio of sub- solution is 1g：1~200mL, preferably 1g：10~100mL.
Bioactive polymer material is chitosan, collagen, polyvinylpyrrolidone, poly butyric ester or gathers oneself
Lactone.Bioactive polymer water, hydro carbons, alcohols, acids or esters dissolving；It is preferred that, it is 0.1% with water or volume fraction
~50% acetum dissolving；It is furthermore preferred that acetum volume fraction is 0.5%~10%.
It is preferred that, bioactive polymer solution is acetum, collagen aqueous solution or the alcoholic solution of chitosan, gathered
The vinylpyrrolidone aqueous solution or alcoholic solution；Its concentration is 2g/L~saturated solution, preferably 25g/L~saturated solution.
In step (1), ultrasound removes the bubble in mixed slurry.
In step (2), mixed slurry can be placed in mould and be freeze-dried shaping.5min is freeze-dried at -80~0 DEG C
~360hr, drying time preferably is 1~120hr；It is furthermore preferred that being freeze-dried under 0.1pa~10Kpa vacuum conditions.
The three-dimensional porous composite of nanometer biological glass obtained after step (2) freeze-drying shaping is washed to neutrality.
It is preferred that, the composite porous use of nanometer biological glass/polymer three-dimensional that step (2) freeze-drying shaping is obtained
Alkaline solution processing, washing to neutrality.
It is preferred that, when bioactive polymer solution is acidity, the nanometer life obtained after step (2) freeze-drying shaping
Thing glass/polymer three-dimensional is composite porous to be handled with alkaline solution, washing to neutrality.
Alkaline solution is that concentration is 0.002M~saturation NaOH, Na2CO3、NaHCO3、KOH、K2CO3、KHCO3Or Ca
(OH)2Deng solution, preferably 0.2~5M NaOH or KOH.6 be immersion, and soak time is 1min~15 day.
The porous microsphere shape nanometer biological glass of the rare earth doped element is prepared by the following method：
(a) at 20~50 DEG C, surfactant is dissolved in alcohol-water mixture, in the alcohol-water mixture, alcohol with
The volume ratio of water is 1：0.2~1；Described alcohol is methanol, ethanol, propyl alcohol, butanol or its any mixture；
Alkali, esters of silicon acis, phosphate, calcium source, soluble rare-earth salt are added, is stirred 3~20 hours；Washing suction filtration takes precipitation；
With SiO2、P2O5、Re2On, CaO meter, esters of silicon acis, phosphate, calcium source, the mol ratio x of soluble rare-earth salt, y, w,
Described in z；
Described alkali is sodium hydroxide, calcium hydroxide, potassium hydroxide or ammoniacal liquor；
Surfactant is cetyl trimethylammonium bromide, P123 or F123, and surfactant contains in reaction system
Measure as 2.5~8mmol/L；
(b) calcined after the precipitation drying that step (a) is obtained at 650~800 DEG C, heating rate is that 1.5~3 DEG C/min is obtained
To bioglass material precursor；
(c) the bioglass material precursor that step (b) is obtained is placed in alkali lye, at 10~50 DEG C etch 15min~
1hr；Described alkali lye is sodium hydroxide, calcium hydroxide, potassium hydroxide solution or ammoniacal liquor.
It is preferred that, in step (a), described alkali is ammoniacal liquor, and ammonia concn is 10~13mol/L, and in reaction system
Content be 0.1~0.2mol/L；Surfactant is cetyl trimethylammonium bromide, and the content in reaction system is 3
~6mmol/L.During calcium source is calcium nitrate, calcium chloride or calcium hydroxide, and reaction system, the content of calcium constituent for 5~
12mmol/L.Esters of silicon acis is tetraethyl orthosilicate or quanmethyl silicate；The content of esters of silicon acis is 40~100mmol/ in reaction system
L；Phosphate is triethyl phosphate or trimethyl phosphate.
It is preferred that, alkali lye is the middle SiO of sodium carbonate liquor, bio-vitric precursor and sodium carbonate in step (c)2Mol ratio
For 1：0.05~0.6；The concentration of sodium carbonate liquor is 6mmol/L~70mmol/L.
By the nanometer biological glass obtained by the above method/polymer three-dimensional porous material, rear-earth-doped is porous micro-
Spherical nanometer biological glass is uniformly attached to the surface of bioactive polymer material porous support；This composite has three-dimensional
The macroporous structure of insertion, with good biocompatibility, biological degradability and osteanagenesis, can be used as bone renovating material.
The advantage of the invention is that：
(1) nanometer biological glass/polymer three-dimensional of the invention is composite porous, uses macromolecule, rear-earth-doped
Nanometer biological glass is used as raw material.Therefore, not only material is cheap and easy to get, materials are extensive and environmentally friendly harmless, technique letter
It is single, it can be operated at room temperature.
(2) nanometer life glass/polymer three-dimensional that prepared by the present invention is composite porous, with three-dimensional porous structure, hole
Gap rate is high, and aperture is big；Its pore size can be adjusted according to polymer concentration；Big pore structure is conducive to osteocyte in timbering material
In growth, it is possible to increase osseointegration character.
(3) nanometer biological glass/polymer three-dimensional porous material for preparing of the present invention, with appropriate mechanical performance and good
It is good can processing type energy, can voluntarily be degraded in human body, with good biocompatibility and biological degradability, also with excellent
The ability of different promotion osteanagenesis, can apply technical field of biological material, be had a good application prospect in bone renovating material field.
Brief description of the drawings
Fig. 1 be embodiment 1,7,8 prepare nanometer biological glass/polymer three-dimensional is composite porous and chitosan
(BGS) XRD picture.
Fig. 2 is the composite porous FTIR images of nanometer biological glass/polymer three-dimensional of the preparation of embodiment 1,7,8.
Fig. 3 (A) (B) is the composite porous SEM image of nanometer biological glass/polymer three-dimensional of the preparation of embodiment 1.
Fig. 4 be embodiment 7 prepare mix cerium nanometer biological glass/polymer three-dimensional it is composite porous cck8 figure.
Instantiation mode
It is following in conjunction with specific embodiments, the present invention is expanded on further.The microspheroidal nano grade biological glass of rare earth doped element
It is prepared by the method that glass material is provided according to 2017100236592 patent applications；Its mean surface pore size is 2~3.5nm, compares surface
Product is 200~300m2/g；Particle diameter is 200~350nm.
Concretely comprise the following steps：(1) in 30 DEG C of tepidarium, take 0.407 (1.12mmol) g cetyl trimethylammonium bromides molten
In 78mL ethanol and the mixed solution of 165mL deionized waters, the conjunction liquid mixed containing cetyl trimethylammonium bromide is formed；
After addition 3mL concentration is stirred 10 minutes for 12mol/L ammoniacal liquor into mixed liquor, 3mL tetraethyl orthosilicates are added
(13.4mmol) is stirred 30 minutes, is then added 0.23mL triethyl phosphates (1.34mmol) and is stirred 30 minutes, adds 0.48g
(2.03mmol) four water-calcium nitrate is stirred 30 minutes；It is eventually adding 0.58g (1.34mmol) lanthanum nitrate hexahydrate to stir 12 hours, takes out
Filter, with deionized water and absolute ethyl alcohol respectively washing 3 times, obtains white precipitate；
(2) white precipitate obtained in (1) is dried in 60 DEG C of baking ovens, (2 DEG C/min) high temperature 650 DEG C in Muffle furnace
Calcining 3 hours, obtains bio-vitric precursor；
(3) natrium carbonicum calcinatum 0.135g (1.27mmol), bio-vitric precursor 0.5g are weighed and (contains SiO2About 6mmol), go
Ionized water 50mL, is placed in 100mL three-necked flasks, etches 30 minutes, is finally centrifuged with 8500r/min in 30 DEG C of water-baths, and
With respectively washing 2 times of deionized water and absolute ethyl alcohol, 60 DEG C of oven dryings are put into, the porous microspheric nanoscale life of lanthanum must be mixed
Thing glass material, its composition can use xSiO2yP2O5wLa2O3ZCaO represents, wherein, x=80%, y=4%, w=4%, z=
12%, its mol ratio is consistent with rate of charge.The resulting porous microsphere shape nano grade biological glass material particle diameter for mixing lanthanum is about
300nm, 245~253m of specific surface area2/ g, surface is distributed the aperture uniformly dissipated, aperture about 2.8nm.
When cetyl trimethylammonium bromide consumption is 0.25g, the resulting porous microsphere shape nano grade biological for mixing lanthanum
Glass material particle diameter about 300nm, 200~206m of specific surface area2/ g, surface is distributed the aperture uniformly dissipated, and aperture is about
3.17nm。
When cetyl trimethylammonium bromide consumption is 0.814g, the resulting porous microsphere shape nano grade biological for mixing lanthanum
Glass material particle diameter about 207nm or so, specific surface area is 278~279m2/ g, surface is distributed the aperture uniformly dissipated, hole
Footpath about 2.03nm.
Lanthanum nitrate can be replaced with ytterbium nitrate, gadolinium nitrate or cerous nitrate, and the porous microsphere shape for mixing ytterbium, gadolinium, cerium is obtained respectively
Nano grade biological glass material.
Porous microsphere shape nano grade biological glass material composition uses xSiO2yP2O5wRe2O3ZCaO is represented, with SiO2、P2O5、
Re2On, CaO meters, esters of silicon acis, phosphate, rare earth element and calcium source molar ratio it is consistent with x, y, w, z, and can adjust.
In following examples, the composition of porous microsphere shape nano grade biological glass material is, x/y=20:1, z/w=2~
10:1, and x+y+w+z=1.
Embodiment 1
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 2%, are stirred complete to chitosan
Acetic acid solution is dissolved in, ultrasound removes bubble removing.Accurately weigh again 1g mix lanthanum microspheroidal nano grade biological glass powder be placed in shell gather
In sugar juice, stirring is uniformly mixed to nanometer biological glass with chitosan solution, and ultrasound removes bubble removing.
It is xSiO to mix lanthanum microspheroidal nano grade biological glass composition2yP2O5wLa2O3ZCaO, wherein, x=80%, y=4%,
W=4%, z=12%；245~253m0000000000 of specific surface area2/ g, aperture about 2.8nm, particle diameter about 300nm.
(2) lanthanum microspheroidal nano grade biological glass/chitosan mixed slurry will be mixed and be transferred to 12mm × 18mm (diameters × height
Degree) in mould, it is placed in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa, you can obtain mixing lanthanum microspheroidal nanoscale
Bio-vitric/chitosan three-dimensional porous material.
Product, which is placed in 1.25mol/L sodium hydroxide solutions, to be soaked 2 hours, and is washed with deionized water to neutrality, produces height
Biocompatibility to mix lanthanum microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.
To mixing lanthanum microspheroidal nano grade biological glass/composite porous shape of chitosan three-dimensional obtained by embodiment 1
Looks and composition are characterized, obtained wide-angle x ray diffraction collection of illustrative plates (XRD), infared spectrum (FTIR) and scanning electron microscope image
(SEM), respectively shown in such as Fig. 1, Fig. 2 and Fig. 3.
Embodiment 2
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 10%, are stirred complete to chitosan
Fully dissolved removes bubble removing in acetic acid solution, ultrasound.1g is accurately weighed again mix lanthanum microspheroidal nano grade biological glass powder be placed in shell
In glycan solution, stirring is uniformly mixed to nanometer biological glass with chitosan solution, and ultrasound removes bubble removing.
It is xSiO to mix lanthanum microspheroidal nano grade biological glass composition2yP2O5wLa2O3ZCaO, wherein, x=80%, y=4%,
W=4%, z=12%；Particle diameter about 300nm, 245~253m of specific surface area2/ g, aperture about 2.8nm.
(2) lanthanum microspheroidal nano grade biological glass/chitosan mixed slurry will be mixed and be transferred to 12mm × 18mm (diameters × height
Degree) in mould, it is placed in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa.
Product, which is placed in 1mol/L sodium hydroxide solutions, to be soaked 1 hour, and is washed with deionized water to neutrality, produces high biology
Compatibility to mix lanthanum microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.
Embodiment 3
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 2%, are stirred complete to chitosan
Acetic acid solution is dissolved in, ultrasound removes bubble removing.Accurately weigh again 1g mix lanthanum microspheroidal nano grade biological glass powder be placed in shell gather
In sugar juice, stirring is uniformly mixed to nanometer biological glass with chitosan solution, and ultrasound removes bubble removing.
It is xSiO to mix lanthanum microspheroidal nano grade biological glass composition2yP2O5wLa2O3ZCaO, wherein, x=80%, y=4%,
W=4%, z=12%；Particle diameter about 207nm or so, specific surface area is 278~279m2/ g, aperture about 2.03nm.
(2) obtained lanthanum microspheroidal nano grade biological glass/chitosan mixed slurry of mixing is transferred to 12mm × 18mm (directly
Footpath × height) in mould, it is placed in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa.
Product, which is placed in 2.5mol/L sodium hydroxide solutions, soaks 30min, and is washed with deionized water to neutrality, produces Gao Sheng
Thing compatibility to mix lanthanum microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.
Embodiment 4
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 2%, are stirred complete to chitosan
Acetic acid solution is dissolved in, ultrasound removes bubble removing.1g is accurately weighed again mixes lanthanum microspheroidal nano grade biological glass powder (be the same as Example
2) it is placed in chitosan solution, stirring is uniformly mixed with chitosan solution to mixing lanthanum microspheroidal nano grade biological glass powder, it is super
Sound removes bubble removing.
(2) obtained lanthanum nano grade biological glass powder/chitosan mixed slurry of mixing is transferred to 12mm × 18mm (diameters
× height) in mould, it is transferred in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa.
Product, which is placed in 1.25mol/L sodium hydroxide solutions, soaks 30min, and is washed with deionized water to neutrality, produces i.e.
High-biocompatibility to mix lanthanum microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.
Embodiment 5
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 2%, are stirred complete to chitosan
Acetic acid solution is dissolved in, ultrasound removes bubble removing.Accurately weigh 2g again mixes lanthanum microspheroidal nano grade biological glass powder (with implementation
Example 1) it is placed in chitosan solution, stirring is uniformly mixed with chitosan solution to mixing lanthanum microspheroidal nano grade biological glass powder,
Ultrasound removes bubble removing.
(2) obtained lanthanum nano grade biological glass powder/chitosan mixed slurry of mixing is transferred to 12mm × 18mm (diameters
× height) in mould, it is placed in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa, you can obtain mixing the life of lanthanum nanoscale
Thing glass/chitosan three-dimensional is composite porous.Lanthanum nano grade biological glass/porous composite wood of chitosan three-dimensional is mixed by obtained
Material, which is placed in 1mol/L sodium hydroxide solutions, to be soaked 3 hours, and is washed with deionized water to neutrality, produces high-biocompatibility
To mix lanthanum microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.
Embodiment 6
(1) accurately weigh 1g collagen powder to be dissolved in 40 DEG C of deionized waters of 25ml, stir complete to collagen
It is dissolved in deionized water, ultrasound removes bubble removing.Accurately weigh 1g again mixes lanthanum microspheroidal nano grade biological glass powder (with real
Apply example 1) it is placed in collagen solution, stirring is to mixing lanthanum microspheroidal nano grade biological glass powder and collagen solution is uniform
Mixing, ultrasound removes bubble removing.
(2) obtained lanthanum nano grade biological glass powder/collagen mixed slurry of mixing is placed on 12mm × 18mm (directly
Footpath × height) in mould, it is transferred in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa.Product is washed with deionized water
Wash to neutrality, or be placed in immersion 1 hour in 0.5mol/L sodium hydroxide solutions, then be washed with deionized water to neutrality, produce i.e.
Obtain high-biocompatibility mixes lanthanum microspheroidal nano grade biological glass/three-dimensional porous composite of collagen.
Embodiment 7
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 2%, are stirred complete to chitosan
Acetic acid solution is dissolved in, ultrasound removes bubble removing.Accurately weigh again 1g mix ytterbium microspheroidal nano grade biological glass powder be placed in shell gather
In sugar juice, stirring is uniformly mixed to nanometer biological glass with chitosan solution, and ultrasound removes bubble removing.
It is xSiO to mix ytterbium microspheroidal nano grade biological glass composition2yP2O5wYb2O3ZCaO, wherein, x=80%, y=4%,
W=4%, z=12%；Particle diameter about 300nm, 240~255m of specific surface area2/ g, aperture about 2.5~3nm.
(2) obtained ytterbium microspheroidal nano grade biological glass/chitosan mixed slurry of mixing is transferred to 12mm × 18mm (directly
Footpath × height) in mould, it is placed in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa.
Product is placed in 1mol/L sodium hydroxide solutions and soaked 20 minutes, is washed with deionized water to neutrality, produces Gao Sheng
Thing compatibility to mix ytterbium microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.
Ytterbium microspheroidal nano grade biological glass/chitosan three-dimensional composite porous pattern and composition is mixed to obtained
Characterized, obtained wide-angle x ray diffraction collection of illustrative plates (XRD) and infared spectrum (FTIR) difference is as depicted in figs. 1 and 2.
Embodiment 8
(1) the accurate 1g chitosans that weigh are placed in the acetic acid solution that 25mL volume fractions are 2vt.%, stirring to chitosan
Acetic acid solution is dissolved completely in, ultrasound removes bubble removing.1g is accurately weighed again mix cerium microspheroidal nano grade biological glass powder be placed in
In chitosan solution, stirring is uniformly mixed to nanometer biological glass with chitosan solution, and ultrasound removes bubble removing.
It is xSiO to mix cerium microspheroidal nano grade biological glass composition2yP2O5wCe2O3ZCaO, wherein, x=80%, y=4%,
W=4%, z=12%, i.e. w/z=3；Particle diameter about 300nm, 240~255m of specific surface area2/ g, aperture about 2.5~3nm.
(2) obtained cerium microspheroidal nano grade biological glass/chitosan mixed slurry of mixing is transferred to 12mm × 18mm (directly
Footpath × height) in mould, it is transferred in freeze-dryer, -80 DEG C, be freeze-dried 48h under 1~2Pa.
Product is placed in 1.5mol/L sodium hydroxide solutions and soaks 30min, deionized water is washed till neutrality, high biology is produced
Compatibility to mix cerium microspheroidal nano grade biological glass/chitosan three-dimensional composite porous.Cerium microspheroidal is mixed to obtained
Nano grade biological glass/composite porous pattern of chitosan three-dimensional and composition are characterized, and obtain wide-angle x ray diffration pattern x
Compose (XRD) and infared spectrum (FTIR) as depicted in figs. 1 and 2.
Ce is taken in addition2O3, (w/z is respectively 1 to the different cerium microspheroidal nano grade biological glass of mixing of CaO mol ratios：5、1：7),
It is made that to mix cerium microspheroidal nano grade biological glass/chitosan three-dimensional composite porous as stated above, and carries out cell experiment,
The cck8 figures of cell are obtained, by as shown in Figure 4.Be respectively the 1st from left to right, 3,7 days when, different Ce2O3, CaO mol ratios (1：
3、1：5、1：7) composite and the result of blank control.Cell inoculum concentration is 5000, adds about 0.08g bio-vitrics.
As a result show, the cytotoxicity of resulting three-dimensional porous composite is low, and bio-compatibility is good, can promote cell
Growth.
The polymer three-dimensional porous material of embodiment 1~8, the macroporous structure with insertion, its large aperture is 5~500 μm,
Porosity 40%~90%.
Claims (10)
1. a kind of nanometer biological glass/polymer three-dimensional porous material, it is characterised in that using bioactive polymer as filling material
Material, the porous microsphere shape nanometer biological glass of rare earth doped element is support；With three-dimensional porous structure, its large aperture is 5~
500 μm, porosity 40%~90%.
2. nanometer biological glass described in claim 1/polymer three-dimensional porous material, it is characterised in that described is rare earth doped
The mean surface pore size of the porous microsphere nanometer biological glass material of element is 2~3.5nm, and specific surface area is 200~300m2/
g；Consisting of xSiO2yP2O5wRe2O3zCaO；
Wherein Re is thulium, selected from ytterbium, gadolinium, cerium or lanthanum；W, x, y, z are mole percent, 0<X≤80%, 0<y≤
10%, 0<Z≤36%, 0<W≤18%, w+x+y+z=1；
Described bioactive polymer be chitosan, collagen, polyvinylpyrrolidone, poly butyric ester, gather oneself in
Ester or any mixture.
3. the preparation method of nanometer biological glass described in claim 1 or 2/polymer three-dimensional porous material, it is characterised in that step
Suddenly include：
(1) the porous microsphere shape nano grade biological glass of rare earth doped element is taken uniformly to be mixed with bioactive polymer solution,
Obtain mixed slurry；
(2) mixed slurry freeze-drying shaping, is made rare earth mixing with nano bio-vitric/polymer three-dimensional composite porous.
4. the preparation method of nanometer biological glass described in claim 3/polymer three-dimensional porous material, it is characterised in that biological
The solvent of living polymer solution is water, hydro carbons, alcohols, acids, esters, alcohols or its mixture；Wherein bioactivity is high
The content of molecule is 5g/L~saturated solution.
5. the preparation method of nanometer biological glass described in claim 3/polymer three-dimensional porous material, it is characterised in that doping
The porous microsphere shape nanometer biological glass of rare earth element and the mass ratio of bioactive polymer are 1：0.1~10；It is rare earth doped
The porous microsphere shape nanometer biological glass of element is 1g with the amount ratio of bioactive polymer solution：1~200mL.
6. the preparation method of nanometer biological glass described in claim 3/polymer three-dimensional porous material, it is characterised in that doping
The porous microsphere shape nanometer biological glass of rare earth element and the mass ratio of bioactive polymer are 1：0.3~5；Rare earth doped member
The porous microsphere shape nanometer biological glass of element is 1g with the amount ratio of bioactive polymer solution：10~100mL.
7. the preparation method of nanometer biological glass described in claim 3/polymer three-dimensional porous material, it is characterised in that step
(2) the composite porous washing of rare earth mixing with nano bio-vitric/polymer three-dimensional after shaping is freeze-dried to neutrality；
When bioactive polymer solution is acidity, rare earth mixing with nano bio-vitric/polymer three-dimensional is composite porous to be used
Alkaline solution is handled and washed to neutrality.
8. the preparation method of nanometer biological glass described in claim 3/polymer three-dimensional porous material, it is characterised in that described
The porous microsphere shape nano grade biological glass of rare earth doped element is prepared by the following method：
(a) at 20~50 DEG C, surfactant is dissolved in alcohol-water mixture, in the alcohol-water mixture, alcohol and water
Volume ratio is 1：0.2~1；Described alcohol is methanol, ethanol, propyl alcohol, butanol or its any mixture；
Alkali, esters of silicon acis, phosphate, calcium source, soluble rare-earth salt are added, is stirred 3~20 hours；Washing suction filtration takes precipitation；
With SiO2、P2O5、Re2On, CaO meter, esters of silicon acis, phosphate, calcium source, the mol ratio of soluble rare-earth salt such as claim
Described in 2 x, y, w, z；
Described alkali is sodium hydroxide, calcium hydroxide, potassium hydroxide or ammoniacal liquor；
Surfactant is that the content of surfactant in cetyl trimethylammonium bromide, P123 or F123, reaction system is
2.5~8mmol/L；
(b) calcined after the precipitation drying that step (a) is obtained at 650~800 DEG C, heating rate is that 1.5~3 DEG C/min is given birth to
Thing glass material precursors；
(c) the bioglass material precursor that step (b) is obtained is placed in alkali lye, and 15min~1hr is etched at 10~50 DEG C；Institute
The alkali lye stated is sodium hydroxide, calcium hydroxide, potassium hydroxide solution or ammoniacal liquor.
9. the preparation method of nanometer biological glass described in claim 8/polymer three-dimensional porous material, it is characterised in that step
(a) in, described alkali is ammoniacal liquor, and ammonia concn is 10~13mol/L, and the content in reaction system is 0.1~0.2mol/
L；Described surfactant is cetyl trimethylammonium bromide, and the content in reaction system is 3~6mmol/L；
During described calcium source is calcium nitrate, calcium chloride or calcium hydroxide, and reaction system, the content of calcium constituent for 5~
12mmol/L；
Described esters of silicon acis is tetraethyl orthosilicate or quanmethyl silicate；The content of esters of silicon acis is 40~100mmol/ in reaction system
L；Phosphate is triethyl phosphate or trimethyl phosphate；
Alkali lye is the middle SiO of sodium carbonate liquor, bio-vitric precursor and sodium carbonate in step (c)2Mol ratio be 1：0.05~
0.6；The concentration of sodium carbonate liquor is 6mmol/L~70mmol/L.
10. nanometer biological glass described in claim 1 or 2/polymer three-dimensional porous material is in terms of bone renovating material is prepared
Using.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109091703A (en) * | 2018-08-08 | 2018-12-28 | 上海师范大学 | A kind of white phosphorus mine of the rare earth doped element/three-dimensional porous composite material of gelatin, preparation method and application |
| CN109134915A (en) * | 2018-07-26 | 2019-01-04 | 上海师范大学 | A kind of three-dimensional porous composite material of RE phosphate/bioactive polymer, preparation method and application |
| CN109745581A (en) * | 2018-12-12 | 2019-05-14 | 华南理工大学 | A kind of bioactivity glass containing multi-stage porous/poly lactide-glycolide acid compound rest and preparation method thereof |
| CN112156226A (en) * | 2020-09-03 | 2021-01-01 | 赣南医学院 | Zinc-doped porous bioactive glass ceramic and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120730A (en) * | 1975-02-20 | 1978-10-17 | Battelle Memorial Institute | Biocompatible ceramic glass |
| CN1836740A (en) * | 2006-04-21 | 2006-09-27 | 华南理工大学 | Composite tri-dimensional porous bone tissue engineering stent material and its preparation method and uses |
| CN1840493A (en) * | 2005-12-30 | 2006-10-04 | 四川大学 | Preparation of magnetic glass ceramics with bioactivity by rare-earth doping |
| WO2011116112A2 (en) * | 2010-03-16 | 2011-09-22 | Lehigh University | Fabrication of porous glass bioscaffolds by sol-gel and polymer sponge methods |
| CN102294049A (en) * | 2011-09-05 | 2011-12-28 | 祝少博 | Bioactive glass and chitosan composite bone repair material and preparation method and application thereof |
| CN105194730A (en) * | 2015-11-09 | 2015-12-30 | 上海师范大学 | Hydrotalcite/chitosan three-dimensional porous bracket and preparation method thereof |
| CN105399335A (en) * | 2015-11-18 | 2016-03-16 | 天津工业大学 | Lanthanum-doped mesoporous bioactive glass, and preparation method and application thereof |
-
2017
- 2017-04-19 CN CN201710258483.9A patent/CN107308499A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120730A (en) * | 1975-02-20 | 1978-10-17 | Battelle Memorial Institute | Biocompatible ceramic glass |
| CN1840493A (en) * | 2005-12-30 | 2006-10-04 | 四川大学 | Preparation of magnetic glass ceramics with bioactivity by rare-earth doping |
| CN1836740A (en) * | 2006-04-21 | 2006-09-27 | 华南理工大学 | Composite tri-dimensional porous bone tissue engineering stent material and its preparation method and uses |
| WO2011116112A2 (en) * | 2010-03-16 | 2011-09-22 | Lehigh University | Fabrication of porous glass bioscaffolds by sol-gel and polymer sponge methods |
| CN102294049A (en) * | 2011-09-05 | 2011-12-28 | 祝少博 | Bioactive glass and chitosan composite bone repair material and preparation method and application thereof |
| CN105194730A (en) * | 2015-11-09 | 2015-12-30 | 上海师范大学 | Hydrotalcite/chitosan three-dimensional porous bracket and preparation method thereof |
| CN105399335A (en) * | 2015-11-18 | 2016-03-16 | 天津工业大学 | Lanthanum-doped mesoporous bioactive glass, and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134915A (en) * | 2018-07-26 | 2019-01-04 | 上海师范大学 | A kind of three-dimensional porous composite material of RE phosphate/bioactive polymer, preparation method and application |
| CN109134915B (en) * | 2018-07-26 | 2021-06-25 | 上海师范大学 | Rare earth phosphate/bioactive polymer three-dimensional porous composite material, and preparation method and application thereof |
| CN109091703A (en) * | 2018-08-08 | 2018-12-28 | 上海师范大学 | A kind of white phosphorus mine of the rare earth doped element/three-dimensional porous composite material of gelatin, preparation method and application |
| CN109091703B (en) * | 2018-08-08 | 2021-06-25 | 上海师范大学 | Rare earth element doped white phosphorus ore/gelatin three-dimensional porous composite material, and preparation method and application thereof |
| CN109745581A (en) * | 2018-12-12 | 2019-05-14 | 华南理工大学 | A kind of bioactivity glass containing multi-stage porous/poly lactide-glycolide acid compound rest and preparation method thereof |
| CN112156226A (en) * | 2020-09-03 | 2021-01-01 | 赣南医学院 | Zinc-doped porous bioactive glass ceramic and preparation method thereof |
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