CN104189953B - Sodium alginate-zein/nanometer hydroxyapatite Composite Bone recovery support and preparation method thereof - Google Patents
Sodium alginate-zein/nanometer hydroxyapatite Composite Bone recovery support and preparation method thereof Download PDFInfo
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- CN104189953B CN104189953B CN201410400242.XA CN201410400242A CN104189953B CN 104189953 B CN104189953 B CN 104189953B CN 201410400242 A CN201410400242 A CN 201410400242A CN 104189953 B CN104189953 B CN 104189953B
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- sodium alginate
- zein
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- nanometer hydroxyapatite
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Abstract
The invention discloses sodium alginate zein/nanometer hydroxyapatite Composite Bone recovery support, remember according to mass percent, including sodium alginate, zein, hydroxyapatite.The invention also discloses preparation method, step includes: forms sodium alginate zein solution after being mixed with zein solution by sodium alginate soln, adds Ca2+Solution forms sodium alginate zein pluralgel, adds PO4 3‑Solution mineralising forms sodium alginate zein/nanometer hydroxyapatite Composite Bone recovery support.The beneficial effects of the present invention is, utilize biocompatibility and degradability that sodium alginate (SA), zein (zein) and hydroxyapatite (HA) are good, by gel is compound and two kinds of means joint mappings of biomimetic mineralization go out sodium alginate zein/nanometer hydroxyapatite porous support materials.
Description
Technical field
The present invention relates to a kind of bone repairing support and preparation method thereof, especially sodium alginate-jade
Rice prolamin/nanometer hydroxyapatite Composite Bone recovery support and preparation method thereof.
Background technology
Natural biomineralization process gives the nanometer hydroxyapatite that osseous tissue camber is orderly
(HAp) the multistage assembling unique with collagen fiber, so that natural bone has the mechanicalness of excellence
Can (high intensity, high rigidity and high tenacity) and biological function [R.Murugan, S.
Ramakrishna.Compos.Sci.Technol.2005,65:2385-2406】.Inspired by this,
People have utilized biomimetic mineralization principle to build aspect and the natural bones such as composition, structure and biological property
Similar nanometer hydroxyapatite/high-molecular biologic compound support frame material is also applied to bone injury
Treatment and reparative experiment.
Substantial amounts of biological evidences shows: as the regulation and control template protein of biomineralization and many
The biomacromolecules such as sugar form gel-like matrix network often through Supramolecular Assembling, and then to life
Thing mineralization process is exerted one's influence [H..Nat.Mater.2010,9:960-961】.Sargassum
Acid sodium (SA) gel has good biocompatibility, easy infiltration, hydrophilic and gelation condition temperature
With etc. feature, in terms of bone tissue engineer, be elected to be Injectable tissue engineered bone by Chinese scholars
The extracellular timbering material of (cartilage) use [Zhu Zhenzong, Liang Weiguo, Shen Yan etc. China's organizational project
Research and clinical rehabilitation .2011,16:2867-2870].Although sodium alginate gel has the most excellent
Point, but its not a kind of preferably timbering material, be primarily present following deficiency: ionomer
The hygroscopic deformation of sodium alginate gel；Ion exchange is easily occurred to lose in ionic medium environment
Gel characteristic causes mechanical strength to reduce；The specificity with cell is lacked on sodium alginate strand
Interaction sites；Simultaneously for the reparation of load position Cranial defect, the power of sodium alginate gel
Learn intensity the most not enough.
Current sodium alginate gel is applied to the method for modifying of imitative bone field of stents and is concentrated mainly on
Biomimetic mineralization [K.Sangeetha, A.Thamizhavel, E.K.Girija.Mater.Lett.
2013,91:27-30.K.D.Son,D.J.Yang,M.S.Kim,et al.Mater.Chem.
Phys.2012,132:1041-1047] and [J.Y.Sun, X.H.Zhao, W.R.K. are blended
Illeperuma, O.Chaudhuri.Nature, 2012,489:133-136.] two aspects.
[M.Rajkumar, N.Meenakshisundaram, the V.Rajendran. such as Rajkumar
Mater.Charact.2011,62:469-479] generate length at sodium alginate gel substrate chats
For the rod-like nano hydroxyapatite (HA) of about 13nm, the power of mineralising composite simultaneously
Performance significantly improves.For sodium alginate gel/hydroxylapatite mineralized compound system,
The inorganic mineral generated clearly enhances mechanical property and the biology performance of material, but does not drop
The hydrophilic of low material, between mineral and sodium alginate substrate, limited combination is difficult to effectively stop simultaneously
Calcium loss.[L.Xie, M.Jiang, X.Dong, the et al.J.Appl.Polym.Sci. such as Xie
2012,124:823-831] use two step cross-linking methods to be prepared for having certain viscoelastic polyethylene
Alcohol/sodium alginate pluralgel, Xiao Haijun etc. [Xiao Haijun, Xue Feng, He Zhi are quick. China's group
Knit engineering research and clinical rehabilitation 2011,15:7113-7117.] and Lan little Yong etc. [Lan little Yong, all
Just pine, Tian Jing etc. Chinese Academy of Medical Sciences journal .2009,31:459-463] use chitosan,
The macromolecular materials such as collagen have carried out the research of similar co-mixing system.Although the power of gel after compound
Performance increases, but there is also that some are clearly disadvantageous, as difficult degradation in PVA body,
Chitosan hydrophilic easily causes the most by force the more large deformation of pluralgel, animal collagen easily causes allos
Property rejection etc., the binding ability of the most simple macromolecule pluralgel is relatively poor.
In view of gel is combined the limitation with two kinds of means of biomimetic mineralization and effectiveness, the present invention combines
Two kinds of methods build three dimensional structure is stable, mechanical strength is high, biological activity is good sodium alginate-
Zein pluralgel mineralising support.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of sodium alginate-molten egg of Semen Maydis alcohol
In vain/nanometer hydroxyapatite Composite Bone recovery support, utilizes sodium alginate (SA), Semen Maydis alcohol molten
Albumen (zein) and the good biocompatibility of hydroxyapatite (HA) and degradability are logical
Cross that gel is compound and two kinds of means joint mappings of biomimetic mineralization go out sodium alginate-zein/
Nanometer hydroxyapatite porous support materials.
The present invention is achieved through the following technical solutions.
A kind of sodium alginate-zein/nanometer hydroxyapatite Composite Bone recovery support,
Remember according to mass percent, including sodium alginate, zein, hydroxyapatite.
Wherein the percentage composition of sodium alginate is 50～90%, and the percentage composition of zein exists
5～25%, the percentage composition of hydroxyapatite is 5～25%.
Further, it is combined by gel between above-mentioned sodium alginate and above-mentioned zein
Build.
Further, above-mentioned hydroxyapatite is that biomimetic mineralization generates.
Further, above-mentioned hydroxyapatite is at above-mentioned sodium alginate and the above-mentioned molten egg of Semen Maydis alcohol
After white gel is compound, biomimetic mineralization builds.
The two of the technical problem to be solved in the present invention are to provide a kind of sodium alginate-molten egg of Semen Maydis alcohol
The preparation method of in vain/nanometer hydroxyapatite Composite Bone recovery support, step includes: by Sargassum
It is molten that acid sodium solution forms sodium alginate-zein after mixing with zein solution
Liquid, adds Ca2+Solution forms sodium alginate-zein pluralgel, adds PO4 3-
Solution forms sodium alginate-zein/nanometer hydroxyapatite Composite Bone recovery support.
Further, concrete steps include:
It is respectively configured sodium alginate soln, 1～the jade of 30mg/mL that concentration is 5～50mg/mL
Rice prolamin solution, Ca2+Solution and PO4 3-Solution；
Fill after sodium alginate soln and zein solution are sufficiently mixed at 40～70 DEG C
Enter bag filter, then bag filter is put into Ca2+Solution left standstill 12～24h obtains sodium alginate-Semen Maydis
Alcohol soluble protein pluralgel；
Sodium alginate-zein pluralgel is put into PO4 3-Solution carries out bionical ore deposit
Change 5～24h and prepare sodium alginate-zein/nanometer hydroxyapatite pluralgel support
Material；
Wherein, remembering according to mass percent, the percentage composition of sodium alginate is 50～90%, beautiful
The percentage composition of rice prolamin is 5～25%, and the percentage composition of hydroxyapatite is 5～25%.
Ca2+Solution can be, but not limited to, CaCl2Solution, solution C a (NO3)2Solution, only
If the conventional solution of calcium ions.
PO4 3-Solution can be, but not limited to, Na3PO4Solution, K3PO4Solution.As long as
The conventional solution of phosphorous acid group example.
Bag filters etc. are buied from market, and hydroxyapatite is to occur mineralising raw in gel rubber system
Become.
Further, above-mentioned PO4 3-PH value of solution >=10.
Beneficial effects of the present invention:
Hydrophobicity and the higher mechanical strength of zein can improve sodium alginate gel
Surface nature, improve gel mechanical performance and increase gel structure stability；
Zein nanosphere surface rich in active group can increase sodium alginate coagulate
The avtive spot of glue biomimetic mineralization, increases the inorganic mineral interaction with gel-type vehicle more to have
The mechanics realizing to effect inorganic nano Mineral pairs pluralgel strengthens；
Nanometer hydroxyapatite is at the common shadow of active group of zein Yu sodium alginate
Ring lower mineralising growth, the suspension cable anchorage to nano-particle can be realized, will effectively reduce calcium loss；
The most this anchorage effect can affect the spatial arrangements of hydroxyapatite in gel microenvironment；
The compound rest that pluralgel substrate is high to inorganic hydroxyapatite content, mechanical strength is high
There is good toughening effect, the toughness of compound rest can be improved；
It is right that zein ball can be realized by the slow releasing function of packaging medicine and somatomedin
The design of compound rest multifunction.
Accompanying drawing explanation
Fig. 1 is sodium alginate-zein/nanometer hydroxyapatite pluralgel support material
The XRD figure spectrum of material；
Before Fig. 2 is sodium alginate gel and sodium alginate-zein pluralgel mineralising
After ess-strain mechanical test curve.
Detailed description of the invention
Below according to drawings and Examples, the present invention is described in further detail.
The present invention, sodium alginate-zein/nanometer hydroxyapatite Composite Bone reparation is propped up
Frame, remembers according to mass percent, including sodium alginate, zein, hydroxyapatite.
Wherein, build by gel is compound between sodium alginate and zein, hydroxyl phosphorus
Lime stone is that biomimetic mineralization builds after, sodium alginate and zein gel are compound.
Fig. 1 is sodium alginate-zein/nanometer hydroxyapatite pluralgel support material
The XRD figure spectrum of material, with reference to Fig. 1, as can be seen from the figure sodium alginate-zein
/ nanometer hydroxyapatite pluralgel substantially conforms to hydroxy-apatite in the diffraction maximum of 25.8 ° and 32 °
Stone (002) and the characteristic peak in (300) face, illustrate the inorganic mineralising of gained in this gel scaffold material
Thing is mainly hydroxyapatite.
Before Fig. 2 is sodium alginate gel and sodium alginate-zein pluralgel mineralising
After ess-strain mechanical test curve, with reference to Fig. 2, as can be seen from the figure sodium alginate with
The pluralgel that zein is formed improves the mechanical strength of sodium alginate gel, simultaneously
After pluralgel is carried out biomimetic mineralization process, the mechanical strength of pluralgel further improves.
Mechanical test results explanation gel is compound and two kinds of means of biomimetic mineralization can be effectively improved alginic acid
The mechanical strength of sodium gel.
Embodiment 1
Specifically comprising the following steps that of preparation
Step 1, is respectively configured the Semen Maydis of the sodium alginate soln of 20mg/mL, 15mg/mL
Alcohol soluble protein solution, 30mg/mLCaCl2Solution and the Na of pH >=103PO4Solution；
Step 2, by 30mL sodium alginate soln and 6mL zein solution at 50 DEG C
Load bag filter after being sufficiently mixed 3h, then bag filter is put into standing 12h in calcium chloride solution
Obtain pluralgel；
Step 3, puts into pluralgel and carries out the prepared sea of biomimetic mineralization 10h in sodium radio-phosphate,P-32 solution
Sodium alginate-zein/nanometer hydroxyapatite pluralgel timbering material.
Embodiment 2
Specifically comprising the following steps that of preparation
Step 1, is respectively configured the Semen Maydis of the sodium alginate soln of 30mg/mL, 10mg/mL
Alcohol soluble protein solution, 20mg/mLCa (NO3)2Solution and the Na of pH >=103PO4Solution；
Step 2, exists 30mL sodium alginate soln and 10mL zein solution
60 DEG C are sufficiently mixed loading bag filter after 3h, are then put in calcium chloride solution by bag filter quiet
Put 12h and obtain pluralgel；
Step 3, puts into pluralgel and carries out the prepared sea of biomimetic mineralization 12h in sodium radio-phosphate,P-32 solution
Sodium alginate-zein/nanometer hydroxyapatite pluralgel timbering material.
Embodiment 3
Specifically comprising the following steps that of preparation
Step 1, is respectively configured the Semen Maydis of the sodium alginate soln of 40mg/mL, 18mg/mL
Alcohol soluble protein solution, 20mg/mLCaCl2Solution and the K of pH >=103PO4Solution；
Step 2, exists 30mL sodium alginate soln and 10mL zein solution
70 DEG C are sufficiently mixed loading bag filter after 2h, are then put in calcium chloride solution by bag filter quiet
Put 12h and obtain pluralgel；
Step 3, puts into pluralgel and carries out the prepared sea of biomimetic mineralization 24h in sodium radio-phosphate,P-32 solution
Sodium alginate-zein/nanometer hydroxyapatite pluralgel timbering material.
Embodiment 4
Specifically comprising the following steps that of preparation
Step 1, is respectively configured the Semen Maydis of the sodium alginate soln of 40mg/mL, 12mg/mL
Alcohol soluble protein solution, 30mg/mLCa (NO3)2Solution and the Na of pH >=103PO4Solution；
Step 2, exists 40mL sodium alginate soln and 10mL zein solution
50 DEG C are sufficiently mixed loading bag filter after 3h, are then put in calcium chloride solution by bag filter quiet
Put 9h and obtain pluralgel；
Step 3, puts into pluralgel and carries out the prepared sea of biomimetic mineralization 24h in sodium radio-phosphate,P-32 solution
Sodium alginate-zein/nanometer hydroxyapatite pluralgel timbering material.
Embodiment 5
Specifically comprising the following steps that of preparation
Step 1, is respectively configured the Semen Maydis of the sodium alginate soln of 40mg/mL, 20mg/mL
Alcohol soluble protein solution, 30mg/mLCaCl2Solution and the K of pH >=103PO4Solution；
Step 2, exists 40mL sodium alginate soln and 10mL zein solution
70 DEG C are sufficiently mixed loading bag filter after 3h, are then put in calcium chloride solution by bag filter quiet
Put 12h and obtain pluralgel；
Step 3, puts into pluralgel and carries out the prepared sea of biomimetic mineralization 24h in sodium radio-phosphate,P-32 solution
Sodium alginate-zein/nanometer hydroxyapatite pluralgel timbering material.
The present invention, hydrophobicity and the higher mechanical strength of zein can improve alginic acid
The surface nature of sodium gel, the mechanical performance improving gel and increase gel structure stability；Beautiful
Rice prolamin nanosphere surface rich in active group to increase sodium alginate gel bionical
The avtive spot of mineralising, increases inorganic mineral with the interaction of gel-type vehicle with more effectively real
The mechanics of existing inorganic nano Mineral pairs pluralgel strengthens；Nanometer hydroxyapatite is molten at Semen Maydis alcohol
Albumen and mineralising growth under the active group joint effect of sodium alginate, can realize nano-particle
Suspension cable anchorage, will effectively reduce calcium loss；The most this anchorage effect can be in gel microenvironment
The middle spatial arrangements affecting hydroxyapatite；Pluralgel substrate is to inorganic hydroxyapatite content
The compound rest high, mechanical strength is high has good toughening effect, can improve the tough of compound rest
Property；Zein ball can be realized multiple by the slow releasing function of packaging medicine and somatomedin
Close the design of support multifunction.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow ripe
The personage knowing this art will appreciate that present invention and is carried out, and can not limit with this
Protection scope of the present invention processed.All equivalences made according to spirit of the invention change or repair
Decorations, all should contain within the scope of the present invention.
Claims (4)
1. sodium alginate-zein/nanometer hydroxyapatite Composite Bone recovery support
Preparation method, it is characterised in that step includes: by sodium alginate soln and zein
Form sodium alginate-zein solution after solution mixing, add Ca2+Solution forms sea
Sodium alginate-zein pluralgel, adds PO4 3-Solution forms sodium alginate-Semen Maydis
Alcohol soluble protein/nanometer hydroxyapatite Composite Bone recovery support；
Step includes:
It is respectively configured sodium alginate soln, 1～the jade of 30mg/mL that concentration is 5～50mg/mL
Rice prolamin solution, Ca2+Solution and PO4 3-Solution；
Fill after sodium alginate soln and zein solution are sufficiently mixed at 40～70 DEG C
Enter bag filter, then bag filter is put into Ca2+Solution left standstill 12～24h obtains sodium alginate-Semen Maydis
Alcohol soluble protein pluralgel；
Sodium alginate-zein pluralgel is put into PO4 3-Solution carries out bionical ore deposit
Change 5～24h and prepare sodium alginate-zein/nanometer hydroxyapatite pluralgel support
Material.
Sodium alginate-zein/nanometer hydroxyapatite the most according to claim 1 is multiple
Close the preparation method of bone repairing support, it is characterised in that described PO4 3-PH value of solution >=10.
Sodium alginate-zein/nanometer hydroxyapatite the most according to claim 2 is multiple
Close the preparation method of bone repairing support, it is characterised in that described Ca2+Solution is CaCl2Solution
Or Ca (NO3)2Solution.
Sodium alginate-zein/nanometer hydroxyapatite the most according to claim 2 is multiple
Close the preparation method of bone repairing support, it is characterised in that described PO4 3-Solution is Na3PO4Molten
Liquid or K3PO4Solution.
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| CN108606993A (en) * | 2018-05-25 | 2018-10-02 | 姜香 | A kind of preparation method of anti-migration type albumen transport agent material |
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