CN106046399A - Preparation method of surface-mineralized chitosan microsphere - Google Patents
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
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- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- 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
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Abstract
The invention relates to a preparation method of a surface-mineralized chitosan microsphere and belongs to the field of medical materials. The preparation method comprises the following steps: (1) preparing a chitosan microsphere by utilizing an emulsion-crosslinking method; (2) configuring a mineralized solution; (3) putting prepared chitosan microsphere powder into the configured mineralized solution to enable mineralization reaction for a certain time at a certain temperature, standing and precipitating, washing and drying to obtain a chitosan microsphere surface-mineralized composite material. A large number of uniformly-dispersed lamellar nano hydroxyapatite crystals are generated on the surface of the chitosan microsphere in situ through a mineralization method. According to the preparation method provided by the invention, under mild conditions, the accurate control of the components, the structure and the content of the nano hydroxyapatite crystals on the surface of the polymer microsphere are realized, so that a bone-like apatite surface with high surface activity and good osteogenetic activity is prepared; the preparation method is stable in process and low in cost and can realize large-scale production. The preparation method provided by the invention has a wide application value in clinical aspect of bone tissue engineering.
Description
Technical field
The present invention relates to the preparation method of a kind of chitosan microball surface mineralising, belong to biomaterial for medical purpose, at osseous tissue
Engineering clinicing aspect has a wide range of applications meaning.
Background technology
Nanometer hydroxyapatite is the main component of human bone inanimate matter, has physicochemical property and effect biology of excellence
Should, it is preferable implantation.But the nanometer hydroxyapatite prepared of traditional method exists that granule is relatively big, dispersion not
Uniformly, have agglomeration and and matrix between the shortcoming such as bond strength is weak, and it is high, difficult to there is also cost in preparation method
With deficiencies such as control, poor repeatability.Mineralising method is to utilize biomineralization mechanism, is mated or chemical bonding by electrostatic with Organic substance
Nucleation and the growth of inorganic nanocrystal is regulated so that Organic substance can combine in situ with inorganic matter nanoparticle etc. mode, thus
Generation and natural minerals have the mineralizing material of analog structure and composition.Therefore nano hydroxyapatite is prepared from the angle of bionic structure
Lime stone crystal can have good biocompatibility and biological function.
Chitosan aboundresources, first has good biocompatibility, biological activity, biodegradability etc. excellent
Objective characteristic；Secondly it can provide specific chemical binding site for nanometer hydroxyapatite, so that hydroxyapatite whisker
Body nucleating growth in situ；Further, chitosan monomer component is glycosaminoglycans, have induction stimulate tissue regeneration rebuild activity and
The effect of promoting bone growing.Therefore chitosan is the most concerned as the research of biomineralization template.
Existing scholar utilizes biomimetic mineralization method to successfully synthesize nano-hydroxyapatite/chitosan composite, and this is combined
Material has had certain improvement on the dispersibility of nanometer hydroxyapatite, particle diameter, agglomeration, also has on composition and structure
There is some feature that nature bone is similar, but effect is not notable, and the increment of nanometer hydroxyapatite has been unable to reach sky
So content needed for inorganic mineral in bone, therefore can not obtain the composition very much like with natural bone tissue and structure.
Summary of the invention
First chitosan is prepared as microsphere by the present invention, improves the specific surface area of chitosan basal body, thus add its with
The joint efficiency of mineral nano hydroxyapatite crystal.It is next real that next utilizes hexamethylenetetramine to decompose slowly control system pH
The mineralising mechanism on existing chitosan microball surface, the beneficially one-tenth of accuracy controlling chitosan microball nano surface hydroxyapatite crystal
Point, structure and content, thus obtain and nature bone extremely analog structure and the inorganic mineral of performance.
The present invention provides to be had and nature bone extremely analog structure and performance and a kind of chitosan microball table with low cost
The preparation method of face mineralising.
The preparation method of a kind of chitosan microball surface mineralising, comprises the steps:
1, liquid paraffin is mixed with surfactant, after stirring, be slowly added to chitosan acetic acid solution, stirring and emulsifying 3 ~ 4 h；,
Form water-in-oil emulsion；Wherein, liquid paraffin is 200 ~ 1000 with chitosan mass ratio；Surfactant and chitosan mass ratio
It is 2 ~ 30；The concentration of chitosan acetic acid solution is 1 wt% ~ 6 wt%.
It is added dropwise over cross-linking agent to cross-link, the emulsion being uniformly mixed.Staticly settle, successively with petroleum ether, different
Propanol rinse, is dried, i.e. prepares chitosan microball.
Described surfactant includes that span80, Tween80, cross-linking agent used include glutaraldehyde, vanillin；Crosslinking
Agent is 0.1 ~ 0.5:1 with chitosan mass ratio；
2, by 1 mol/L, the hexamethylenetetramine of 150 mL, 50 mmol/L, the dibastic sodium phosphate of 50 mL, 125 mmol/L, 50
The calcium chloride of mL is placed in 500 mL volumetric flasks, then to make pH be 4.5 ~ 6, during after fully dissolving, solution is removed in water-bath with HCl regulation
Bubble, is i.e. arranged to mineralized liquid.
3, being well-dispersed in by chitosan microball in configured mineralized liquid, chitosan microball with mineralized liquid mass concentration is
1 ~ 2 g/L, continuous stirring 3 ~ 12 h times of reaction, the solution being uniformly mixed at a temperature of 35 ~ 90 DEG C.Staticly settle, depend on
Secondary deionized water, isopropanol washing precipitation, is dried 10 ~ 12 h, obtains the chitosan microball after mineralising at 50 ~ 60 DEG C.
Through process above step, the epontic nanometer hydroxyapatite of chitosan microball is dispersed, size uniformity,
In the form of sheets or needle-shaped nano-structure.
The present invention is at chitosan microball Surface Creation favorable dispersibility, the lamellar of size uniformity or acicular nanometer hydroxyl phosphorus
Lime stone crystal, it is thus achieved that there is the osteoid apatite surface of high surface and osteogenic activity, the most similar to natural bone tissue
Composition, content and structure of, there is good biological activity and biological function.
Chitosan microball surface can be that nanometer hydroxyapatite provides specific chemical binding site so that hydroxy-apatite
Stone and chitosan microball surface reach nano level In-situ reaction, thus prepare the composite having good stability；Additionally use
Supersaturation calcium phosphate solution is mineralized liquid, comes smart by the pH value slowly decomposing increase solution of hexamethylenetetramine in mineralized liquid
The really structure of regulation and control nanometer hydroxyapatite and pattern, and the continued propagation of beneficially nanometer hydroxyapatite.I.e. form tool
There are good biological activity and the osteoid apatite surface of biological function.
The composite prepared of the present invention is used to have the composition the most similar to natural bone tissue, content and structure of, tool
There are good biological activity and biological function, have a wide range of applications in terms of clinical implantation.
The present invention achieve in a mild condition the composition of polymer microsphere surface nano hydroxyl phosphorite crystal, structure and
The accurate control of its content, prepares the osteoid apatite surface with high surface and good osteogenic activity, process stabilizing,
With low cost, large-scale production can be realized.
Accompanying drawing explanation
Chitosan microball SEM picture prepared by Fig. 1 emulsifying-cross-linking method.
Chitosan microball surface mineralising composite SEM picture prepared by Fig. 2 mineralising method.
Detailed description of the invention
Below in conjunction with the detailed description of the invention by accompanying drawing illustrated embodiment, the foregoing of the present invention is remake further
Describe in detail.But this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to Examples below.Without departing from the present invention
In the case of above-mentioned technological thought, the various replacements made according to ordinary skill knowledge and customary means or change, all should
It is included within the scope of the invention.
Embodiment 1
110 g liquid paraffin and 3 g span80 are mixed, after stirring, are slowly added to the chitosan acetic acid solution of 50 g 2 wt%,
30 DEG C of stirring and emulsifying 3 h, form water-in-oil emulsion.
The glutaraldehyde being added dropwise over 0.0428 g carries out cross-linking 3 h, and the emulsion being uniformly mixed staticly settles；
Add petroleum ether, isopropanol washing precipitation, be dried 10 h at 50 ~ 60 DEG C, obtain chitosan microball, chitosan microball particle diameter
It is 5 ~ 15 μm (see figure 1)s.
0.3 g institute chitosan microball is well-dispersed in the mineralized liquid that 250 mL and pH are 4.5, stirs continuously at 37 DEG C
Mix reaction 3 h, the solution being uniformly mixed.Staticly settle, successively by deionized water, isopropanol washing precipitation, be dried, to obtain final product
Chitosan microball after mineralising, the chitosan microball surface after mineralising is acicular nanometer apatite structure (see figure 2).
Embodiment 2
124.742 g liquid paraffin and 3.858 g span80 are mixed, after stirring, is slowly added to the chitosan of 60 g 4 wt%
Acetic acid solution, 37 DEG C of stirring and emulsifying 3 h, form water-in-oil emulsion.
It is added dropwise over 0.214 g glutaraldehyde to carry out cross-linking 3 h, the emulsion being uniformly mixed.Staticly settle, add stone
Oil ether, isopropanol washing precipitation, be dried 12 h at 50 ~ 60 DEG C.
The chitosan microball of 0.4 g is well-dispersed in the mineralized liquid that 250mL and pH is 5, continuous stirring at 70 DEG C
React 12 h, the solution being uniformly mixed.Staticly settle, successively by deionized water, isopropanol washing precipitation, be dried, to obtain final product
Chitosan microball after mineralising.
Embodiment 3
124.742 g liquid paraffin and 3.858 g span80 are mixed, after stirring, is slowly added to the chitosan of 50 g 4 wt%
Acetic acid solution, 60 DEG C of stirring and emulsifying 3 h, form water-in-oil emulsion.
It is added dropwise over 0.214 g vanillin to carry out cross-linking 3 h, the emulsion being uniformly mixed.Staticly settle, add stone
Oil ether, isopropanol washing precipitation, be dried 11 h at 50 ~ 60 DEG C.
Being well-dispersed in the mineralized liquid that 250 mL and pH are 5.5 by the chitosan microball powder of 0.35 g, 85 DEG C continuously
Stirring reaction 12 h, the solution being uniformly mixed.Staticly settle, successively by deionized water, isopropanol washing precipitation, be dried,
Obtain mineralising chitosan microball.
Embodiment 4
127 g liquid paraffin and 3.5 g tween80 being mixed, the chitosan acetic acid being slowly added to 50 g 3 wt% after stirring is molten
Liquid, 50 DEG C of stirring and emulsifying 4 h, form water-in-oil emulsion.
It is added dropwise over 0.214 g glutaraldehyde to carry out cross-linking 2 h, the emulsion being uniformly mixed.Staticly settle, add stone
Oil ether, isopropanol washing precipitation, be dried 10 h at 50 ~ 60 DEG C.
The chitosan microball powder of 0.4 g is well-dispersed in 250 mL, and pH is in the mineralized liquid of 5.5, and 90 DEG C are stirred continuously
Mix reaction 3 h, the solution being uniformly mixed.Staticly settle, successively by deionized water, isopropanol washing precipitation, be dried, to obtain final product
Chitosan microball after mineralising.
Claims (4)
1. a preparation method for chitosan microball surface mineralising, its step is as follows:
(1) surfactant is added in liquid paraffin, after stirring, add chitosan acetic acid solution, 30 ~ 60 DEG C of stirring and emulsifying 3 ~ 4
H, forms water-in-oil emulsion；The aldehyde crosslinking agent being added dropwise over carries out cross-linking 3 ~ 4 h, the emulsion being uniformly mixed；Stand
Precipitation, is sequentially added into petroleum ether, isopropanol washing precipitation, is dried 10 ~ 12 h, i.e. prepares chitosan microball at 50 ~ 60 DEG C；Used
The concentration of chitosan acetic acid solution be 1 wt% ~ 6 wt%；Liquid paraffin used is 200 ~ 1000:1 with chitosan mass ratio；
Surfactant used is 2 ~ 30:1 with chitosan mass ratio；Aldehyde crosslinking agent used and chitosan mass ratio be 0.1 ~
0.5:1；
(2) 1 mol/L hexamethylenetetramine 150 mL, 50 mmol/L dibastic sodium phosphate 50 mL, 125 mmol/L chlorinations are taken respectively
Calcium 50 mL；It is placed in 500 mL volumetric flasks, is 4.5 ~ 6 with HCl regulation pH value, constant volume, i.e. it is arranged to mineralized liquid；
(3) chitosan microball is well-dispersed in configured mineralized liquid, wherein, chitosan microball and mineralized liquid mass concentration
It is 1 ~ 2 g/L；Continuous stirring reaction 3 ~ 12 h, the solution being uniformly mixed at 35 ~ 90 DEG C；Staticly settle, add go from
Sub-water fully washs precipitation, after centrifugation, by isopropanol washing precipitation, is dried 10 ~ 12 h, obtains mineralising shell at 50 ~ 60 DEG C
Polysaccharide microsphere.
The preparation method of a kind of chitosan microball surface the most according to claim 1 mineralising, is characterized in that described mineralising
The surface in situ of chitosan microball generates substantial amounts of being uniformly dispersed, lamellar or needle nano-hydroxy apatite crystal.
The preparation method of a kind of chitosan microball surface the most according to claim 1 mineralising, is characterized in that described aldehydes is handed over
Connection agent includes glutaraldehyde, vanillin.
The preparation method of a kind of chitosan microball surface the most according to claim 1 mineralising, is characterized in that living in described surface
Property agent includes span80, Tween80.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750394A (en) * | 2016-11-18 | 2017-05-31 | 合肥工业大学 | The controllable method for preparing of uniform particle diameter single dispersing microgel |
| CN111801155A (en) * | 2018-06-21 | 2020-10-20 | 弗门尼舍有限公司 | Method for preparing microcapsules |
| CN114314811A (en) * | 2021-12-28 | 2022-04-12 | 北京建工环境修复股份有限公司 | Iron-carbon composite material and preparation method and application thereof |
| CN114761048A (en) * | 2019-06-14 | 2022-07-15 | 盖斯特里希医药公司 | Collagen matrix or particle blends of bone substitute materials |
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| CN1103849A (en) * | 1993-12-15 | 1995-06-21 | 中国科学院化工冶金研究所 | Method for prepn. of ball shaped hydroxy-apatite with homogeneous precipitation |
| CN101491690A (en) * | 2009-02-16 | 2009-07-29 | 重庆大学 | Preparation method of nano-micron hydroxylapatite powder |
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2016
- 2016-07-20 CN CN201610570320.XA patent/CN106046399A/en active Pending
Patent Citations (2)
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| CN1103849A (en) * | 1993-12-15 | 1995-06-21 | 中国科学院化工冶金研究所 | Method for prepn. of ball shaped hydroxy-apatite with homogeneous precipitation |
| CN101491690A (en) * | 2009-02-16 | 2009-07-29 | 重庆大学 | Preparation method of nano-micron hydroxylapatite powder |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750394A (en) * | 2016-11-18 | 2017-05-31 | 合肥工业大学 | The controllable method for preparing of uniform particle diameter single dispersing microgel |
| CN111801155A (en) * | 2018-06-21 | 2020-10-20 | 弗门尼舍有限公司 | Method for preparing microcapsules |
| CN114761048A (en) * | 2019-06-14 | 2022-07-15 | 盖斯特里希医药公司 | Collagen matrix or particle blends of bone substitute materials |
| CN114314811A (en) * | 2021-12-28 | 2022-04-12 | 北京建工环境修复股份有限公司 | Iron-carbon composite material and preparation method and application thereof |
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