CN110201228A - A kind of calcium phosphate bone cement and its preparation method and application containing decalcified bone matrix - Google Patents
A kind of calcium phosphate bone cement and its preparation method and application containing decalcified bone matrix Download PDFInfo
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- CN110201228A CN110201228A CN201910319769.2A CN201910319769A CN110201228A CN 110201228 A CN110201228 A CN 110201228A CN 201910319769 A CN201910319769 A CN 201910319769A CN 110201228 A CN110201228 A CN 110201228A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
- A61L27/3604—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix characterised by the human or animal origin of the biological material, e.g. hair, fascia, fish scales, silk, shellac, pericardium, pleura, renal tissue, amniotic membrane, parenchymal tissue, fetal tissue, muscle tissue, fat tissue, enamel
- A61L27/3608—Bone, e.g. demineralised bone matrix [DBM], bone powder
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
- A61L27/3641—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix characterised by the site of application in the body
- A61L27/3645—Connective tissue
- A61L27/365—Bones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention belongs to bone injuries to repair biomedical materials field, and in particular to a kind of calcium phosphate bone cement and its preparation method and application containing decalcified bone matrix.The calcium phosphate bone cement is made of solid fraction and liquid phase part, wherein, solid fraction is combined by calcium carbonate, synthos (type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium phosphate dibasic anhydrous, hydroxyapatite) with DBM, and the mass ratio of calcium carbonate, synthos and DBM is 3:10:0.1~3:10:4;And solid-to-liquid ratio is 1:0.4~1:0.6.Calcium phosphate bone cement provided by the present invention containing DBM has good injection-type, anti-collapsibility, osteoconductive, osteoinductive, cell activity and preferable biological degradability, is suitable for orthopedics injuries reparation.
Description
Technical field
The invention belongs to bone injuries to repair biomedical materials field, and in particular to one kind is containing decalcified bone matrix (DBM)
Calcium phosphate bone cement and its preparation method and application.
Background technique
Clinically bone defect patient is caused to increase due to astogeny, tumour, wound, osteomyelitis and bone disease etc. year by year
Add, the demand to bone impairment renovation material increasingly increases.Traditional Bone Defect Repari mode mainly includes the shifting of autologous bone and allograph bone
Plant, but there are immunological rejection, supply source it is limited and the problems such as need second operation.With the development of biomaterial, people
Work bone renovating material is concerned.Calcium phosphate material application form multiplicity, compared to blocks repair materials, calcium phosphate bone cement
(Calcium Phosphate Cements, CPC) has good mobility, self-curing performance and biocompatibility, can be not
It is arbitrarily filled at regular bone defect.Moreover, calcium phosphate bone cement is likely to form interconnected three-dimensional pore space in the filling process
Structure, be conducive to bone tissue grow into and angiogenesis.Voids content, distribution and size in material etc. are to skeletonization and at blood
Pipe has great influence.The phosphate groups on calcium phosphate bone cement surface can also become the site of load bone growth factor.
There is Quickset in foreign countriesTM(Arthrex/Graftys)、Norian SRS(DePuy Synthes)、Pro-
Dense(Wright Medical)、HydroSet(Stryker)、Callos Inject(Acumed)、Ossilix
(Exactech)、CERAMENTTM(Zimmer) the calcium phosphate bone cement launch that international well-known medical apparatus corporation, Ltd releases such as,
Two class of injection-type and face chamotte mould can be divided into according to clinical use scene.QuicksetTM(Arthrex/Graftys)、Pro-
Dense(Wright Medical)、HydroSet(Stryker)、Callos Inject(Acumed)、CERAMENTTM
It (Zimmer) is injection-type product;Then there are two types of dosage forms by Norian SRS (DePuy Synthes), Ossilix (Exactech).
It is analyzed according to the composition of solid-phase component, with alpha-calcium phosphate (α-TCP), hydroxyapatite (HA), calcium deficiency type hydroxyapatite
(CDA), calcium phosphate dibasic anhydrous (DCPA), dicalcium phosphate dihydrate (DCPD), tetracalcium phosphate (TTCP) composition;Liquid phase is with hydroxypropyl first
Base cellulose (HPMC), sodium radio-phosphate,P-32 solution, polyvinylpyrrolidone, sodium silicate solution etc.;In addition there are also trisodium citrates, poly- cream
The additives such as sour fiber.α-TCP, DCPA, TTCP can be rapidly converted into the very poor HA of degradation property in solidification process, deposit in vivo
Staying cannot degrade for a long time.Degradation is added in the application on the basis of type alpha tricalcium phosphate, calcium phosphate dibasic anhydrous, hydroxyapatite
Bata-tricalcium phosphate of good performance, calcium carbonate, can be improved the degradation rate of bone cement in vivo.The calcium carbonate of addition is above-mentioned
The new component not having in product form, it can be to solidify that the calcium ion generated is on the one hand reacted with the citric acid solution in liquid phase
Journey provides calcium source, and the reaction of another aspect citric acid solution generates CO2Gas is constituted loose porous after calcium phosphate bone cement solidifies
Structure further increases its degradation property.Decalcified bone matrix (Demineralized Bone Matrix, DBM) is allogeneic
The product that bone is chilled, degreasing, decalcification, deproteinized are handled, remains the growth factor and glue that can induce bone tissue formation
The matrix such as original.The growth factor B MP that DBM is released can be sticked with mediated cell, and activation signal conduction path, be made from bone
Has the characteristics that the inductivity osteoprogenitor cells of multipotency and Multidirectional Differentiation around membrane fiber layer, blood vessel and in soft tissue to cartilage, skeletonization
The conversion of cell direction, realizes induced osteogenesis.Decalcified bone matrix is light loose, is added in calcium phosphate bone cement, reduces bone cement
Density after solidification further promotes the formation of internal voids structure, increases degradation property.Therefore, building load bone uptake because
Sub (DBM), energy rapid curing can preferably meet clinical demand, benefit patient at porous structure calcium phosphate bone cement, it may have
Good social and economic benefit.
Summary of the invention
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of calcium phosphate bone for containing decalcified bone matrix (DBM)
Cement and its preparation method and application.
For achieving the above object, the technical scheme adopted by the invention is as follows:
One kind containing the calcium phosphate bone cement of decalcified bone matrix (DBM), is made of solid fraction and liquid phase part, the solid phase
Part is combined by calcium carbonate, synthos and DBM, and the liquid phase part is citric acid solution.
In above scheme, the mass ratio of the calcium carbonate, synthos and DBM is 3:10:0.1~3:10:4.
In above scheme, the solid-to-liquid ratio of the solid fraction and liquid phase part is 1:0.4~1:0.6.
In above scheme, the synthos are type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium phosphate dibasic anhydrous and hydroxy-apatite
One or more of stone.
In above scheme, the synthos are type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium phosphate dibasic anhydrous, hydroxy-apatite
The mixture that stone 3:3:3:1~1:1:0.9:0.3 in mass ratio is mixed.
In above scheme, the calcium carbonate is precipitated calcium carbonate and/or powdered whiting.
In above scheme, the concentration of the citric acid solution is 0.5~3mol/L.
In above scheme, sodium alginate and/or chitosan are also contained in the citric acid solution.
In above scheme, the calcium carbonate and synthos be micron level spherical, micron-stage sheet-like, nanoscale it is spherical or
Nano-grade substance.
In above scheme, the DBM is micron level spherical or sheet, grade be spherical or flaky substance.
The preparation method of the above-mentioned calcium phosphate bone cement containing decalcified bone matrix (DBM), include the following steps: by calcium carbonate,
Synthos and DBM are uniformly mixed to form solid-phase complex, stir and evenly mix solid-phase complex and liquid phase part to form bone cement
Lotion, then by lotion, curing molding obtains the bone cement containing DBM under conditions of 37 DEG C, humidity 95%.
The above-mentioned calcium phosphate bone cement containing decalcified bone matrix repairs the application in field in bone injury.
Beneficial effects of the present invention: 1) present invention utilizes the collective effect of calcium carbonate and DBM, increases calcium phosphate bone cement
Internal voids structure after solidification, the density after reducing bone cement solidification, improves its degradation property, realizes osteoacusis work
With;The growth factor B MP that DBM is released simultaneously induces osteoprogenitor cells to convert to cartilage, osteoblast direction, realizes that self-bone grafting is made
With;2) calcium phosphate bone cement of the present invention containing decalcified bone matrix (DBM) has rapid curing, good biocompatibility, degradation
The feature that property is good, bone formation performance is good, can preferably meet clinical demand.
Detailed description of the invention
Fig. 1 is the product X RD analysis after calcium phosphate bone cement external degradation.
Fig. 2 is the test of calcium phosphate bone cement external degradation.
Fig. 3 is the SEM figure of cross section after calcium phosphate bone cement solidifies.
Fig. 4 is the HE stained slice (rat) of calcium phosphate bone cement et al. Ke test.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, the calcium carbonate is commercially available medicinal calcium carbonate, and the commercially available medicinal calcium carbonate is
Heavy or precipitated calcium carbonate [CaCO3];The type alpha tricalcium phosphate (α-TCP) is the type alpha tricalcium phosphate of solid reaction process preparation;Institute
State the bata-tricalcium phosphate that bata-tricalcium phosphate (β-TCP) is solid reaction process preparation;The calcium phosphate dibasic anhydrous (DCPA) is coprecipitated
The calcium phosphate dibasic anhydrous of shallow lake method preparation;The hydroxyapatite (HA) is the nanometer hydroxyapatite of coprecipitation preparation;
Embodiment 1
One kind containing the calcium phosphate bone cement of decalcified bone matrix (DBM), is prepared via a method which to obtain:
(1) 64g citric acid, 1.5g sodium alginate are weighed, above two raw material is added in 10ml deionized water, dissolution,
Liquid phase is obtained, room temperature preservation is spare;
(2) by the powdered whiting of micron level spherical, type alpha tricalcium phosphate (α-TCP), bata-tricalcium phosphate (β-TCP), anhydrous
The DBM 3:3:3:3:1:0.1 in mass ratio of calcium monohydrogen phosphate (DCPA), hydroxyapatite (HA) and micron-stage sheet-like is in small mortar
In uniformly mix, then by solid-to-liquid ratio be 1:0.4 accurate measuring liquid phase, by liquid phase be added solid phase powder in, rapidly after mixing evenly
Inserting length, width and height is that curing molding obtains the calcium phosphate bone water containing DBM under conditions of 37 DEG C, humidity 95% in the mold of 1cm
Mud.
Embodiment 2
One kind containing the calcium phosphate bone cement of decalcified bone matrix (DBM), is prepared via a method which to obtain:
(1) 64g citric acid, 1.5g chitosan are weighed, above two raw material is added in 10ml deionized water, dissolution obtains
To liquid phase, room temperature preservation is spare;
(2) by the powdered whiting of micron level spherical, type alpha tricalcium phosphate (α-TCP), bata-tricalcium phosphate (β-TCP), anhydrous
Calcium monohydrogen phosphate (DCPA), hydroxyapatite (HA) and micron-stage sheet-like DBM 3:3:3:3:1:0.5 in mass ratio are in small mortar
Uniformly mixing, then pressing solid-to-liquid ratio is 1:0.5 accurate measuring liquid phase, and liquid phase is added in solid phase powder, is filled out after mixing evenly rapidly
Entering length, width and height is that curing molding obtains the calcium phosphate bone water containing DBM under conditions of 37 DEG C, humidity 95% in the mold of 1cm
Mud.
Embodiment 3
One kind containing the calcium phosphate bone cement of decalcified bone matrix (DBM), is prepared via a method which to obtain:
(1) 32g citric acid, 2.0g chitosan are weighed, above two raw material is added in 10ml deionized water, dissolution obtains
To liquid phase, room temperature preservation is spare;
(2) by the precipitated calcium carbonate of micron level spherical, type alpha tricalcium phosphate (α-TCP), bata-tricalcium phosphate (β-TCP), anhydrous
Calcium monohydrogen phosphate (DCPA), hydroxyapatite (HA) and grade sheet DBM 3:3:3:3:1:2.0 in mass ratio are in small mortar
Uniformly mixing, then pressing solid-to-liquid ratio is 1:0.6 accurate measuring liquid phase, and liquid phase is added in solid phase powder, is filled out after mixing evenly rapidly
Entering length, width and height is that curing molding obtains the calcium phosphate bone water containing DBM under conditions of 37 DEG C, humidity 95% in the mold of 1cm
Mud.
Calcium phosphate bone cement cylinder of the present invention preparation gained containing DBM is subjected to external degradation test, after degrading 160 days
With do not carry out external degradation test sample drying after carry out XRD analysis (see Fig. 1), as the result is shown external degradation test sample
Type alpha tricalcium phosphate and calcium carbonate content reduce in product, and hydroxyapatite content increases, and show type alpha tricalcium phosphate and calcium carbonate to hydroxyl
Base apatite is converted.It is drawn the qualitative data of external degradation test specimen (see Fig. 2), the results show that of the invention
For preparation gained calcium phosphate bone cement cylinder sample at 160 days, degradation rate can reach 29.6%, and degradation rate is very fast.To this hair
Scanning electron microscopic observation is carried out after calcium phosphate bone cement cylinder sample drying obtained by bright preparation (see Fig. 3), it is seen that a large amount of 100~500 μ
The gap of m, the gap are by calcium carbonate and the coefficient result of DBM.Prepared by gained calcium phosphate bone cement sample to the present invention
It carries out Rat calvarial Implantation Test (see Fig. 4), calcium phosphate bone cement sample has good bio-compatible in vivo as the result is shown
Property, energy fast degradation is simultaneously converted into new bone.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (10)
1. a kind of calcium phosphate bone cement containing decalcified bone matrix, which is characterized in that it is made of solid fraction and liquid phase part, it is described
Solid fraction is combined by calcium carbonate, synthos and DBM, and the liquid phase part is citric acid solution.
2. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the calcium carbonate, phosphorus
The mass ratio of acid calcium salt and DBM are 3: 10: 0.1 ~ 3: 10: 4.
3. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the solid fraction and
The solid-to-liquid ratio of liquid phase part is 1: 0.4 ~ 1: 0.6.
4. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the synthos are
One or more of type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium phosphate dibasic anhydrous and hydroxyapatite.
5. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the synthos are
Type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium phosphate dibasic anhydrous, hydroxyapatite in mass ratio 3: 3: 3: 1 ~ 1: 1:
0.9: 0.3 mixture mixed.
6. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the calcium carbonate is light
Matter calcium carbonate and/or powdered whiting.
7. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the citric acid solution
Concentration be 0.5 ~ 3 mol/L;Also contain sodium alginate and/or chitosan in the citric acid solution.
8. the calcium phosphate bone cement according to claim 1 containing decalcified bone matrix, which is characterized in that the calcium carbonate and phosphorus
Acid calcium salt is that micron level spherical, micron-stage sheet-like, nanoscale be spherical or nano-grade substance;The DBM is micron level spherical
Or sheet, grade be spherical or flaky substance.
9. the preparation method of any calcium phosphate bone cement containing decalcified bone matrix of claim 1 ~ 8, which is characterized in that including
Following steps: calcium carbonate, synthos and DBM are uniformly mixed to form solid-phase complex, by solid-phase complex and liquid phase part
It stirs and evenly mixs to form bone cement lotion, then by lotion, curing molding is obtained containing DBM's under conditions of 37 DEG C, humidity 95%
Bone cement.
10. the application that any calcium phosphate bone cement containing decalcified bone matrix of claim 1 ~ 8 repairs field in bone injury.
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Cited By (1)
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