CN103691002A - Bacterial cellulose/collagen/hydroxyapatite composite material, and preparation and application thereof - Google Patents
Bacterial cellulose/collagen/hydroxyapatite composite material, and preparation and application thereof Download PDFInfo
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- CN103691002A CN103691002A CN201310693831.7A CN201310693831A CN103691002A CN 103691002 A CN103691002 A CN 103691002A CN 201310693831 A CN201310693831 A CN 201310693831A CN 103691002 A CN103691002 A CN 103691002A
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- collagen
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- hydroxyapatite
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Abstract
The invention discloses a bacterial cellulose/collagen/hydroxyapatite composite material and a preparation method thereof. In the method, the capillary force of internal pores and an ultrasonic-assisted collagen molecule diffusion method are adopted, a bacterial cellulose dry film, collagen, procyanidine, CaCl2 and simulated body fluid are taken as raw materials, and the mass ratio of the bacterial cellulose dry film to the collagen to the procyanidine to CaCl2 is (10-200):(1-50):(4-6):(6-10); the collagen is uniformly distributed in the network structure of the bacterial cellulose in an irregular shape, and the obtained compound is prepared into the bacterial cellulose/collagen/hydroxyapatite composite material by adopting a biomimetic mineralization method. The composite material disclosed by the invention has superior mechanical property and a unique three-dimensional nano-network structure, is more similar to human skeletal tissues on the aspects of structure and component, and is expected to meet the application requirement of a skeletal tissue engineering stent material.
Description
Technical field
The present invention relates to a kind of Bacterial cellulose/collagen/hydroxyapatite composite and preparation method thereof.
Background technology
Biomaterial is as one of current era four large new materials, and its development is closely bound up with the mankind's health, thereby has been subject to increasing concern and research.Tissue engineering bracket is as a kind of large focus that has just like become scientific research and clinical practice of biomaterial.At present, for tissue engineering bracket research and the material of application, mainly comprise collagen, chitosan, polylactic acid and alginate etc.Compare with these biomaterials, Bacterial cellulose has the character of many uniquenesses, as natural hyperfine three-dimensional net structure, excellent mechanical property, the moisture holding capacity of superelevation, good biocompatibility etc., because being widely used in wound dressing, artificial skin, artificial blood vessel, the aspects such as artificial cornea.
Aspect cartilage tissue engineering rack, because Bacterial cellulose has the mechanical strength approaching with cartilaginous tissue and good cell adhesion, the cartilage tissue engineering rack development that the Bacterial cellulose of take is matrix rapidly.For example, CN101947335A " bacteria cellulose/gelatin/hydroxyapatite composite material and preparation method thereof " has reported a kind of bacteria cellulose/gelatin/hydroxyapatite composite material, and this composite has good biocompatibility and mechanical property, yet because skeleton is mainly comprised of collagen and hydroxyapatite, although gelatin is the catabolite of collagen, its amino composition is similar with collagen, but gelatin is micromolecule eventually, the biological nature of collagen cannot be really shown, if be applied to, clinically still biological rejection may be caused.In other one side, compositing characteristic in view of skeleton, many scholars are also studied for collagen/hydroxyapatite composite, and find that this composite not only has and the similar structure of nature bone, and its biological activity is good, but the problem that ubiquity mechanical property is poor, has limited the further application of material.Defect based on above two aspect researchs, consider mechanical property and collagen/hydroxyapatite composite and the similar composition characteristic of skeleton that Bacterial cellulose is good, if prepare a kind of novel Bacterial cellulose/collagen/hydroxyapatite composite by the two being combined someway, it will not only can solve the poor problem of traditional collagen/hydroxyapatite composite materials property, and it will simulate human skeleton compositing characteristic better with respect to bacteria cellulose/gelatin/hydroxyapatite composite material, there is more importantly clinical value.And this novel Bacterial cellulose/collagen/hydroxyapatite composite structure uniform component in order to make to synthesize, its precondition is exactly first to prepare the Bacterial cellulose/collagen composite materials of constituent homogeneous.To this, CN102600507A " in a kind of cell culturing rack material and preparation method thereof " has reported and a kind ofly by dipping, has prepared Bacterial cellulose/collagen composite materials method, but because collagen belongs to biomacromolecule, be difficult to enter the nanometer space of Bacterial cellulose, therefore in the Bacterial cellulose/collagen composite materials obtaining by the method, collagen distribution is very inhomogeneous, is only present in Bacterial cellulose surface.
In view of above background, the present invention adopts the Bacterial cellulose thin film of porous after drying as matrix first, by the capillary force action of its internal void and utilize ultrasonic accessory molecule diffusion method, impel collagen can fully enter the nanometer space of Bacterial cellulose thin film, thereby obtain the Bacterial cellulose/collagen composite materials of collagen distributed components, and further this material soaking is processed and finally obtained Bacterial cellulose/collagen/hydroxyapatite composite by biomimetic mineralization in simulated body fluid.This material composition homogeneous, not only there is the composite nanostructure with the similar collagen/hydroxyapatite of nature bone, and solved the lower difficult problem of traditional collagen/hydroxyapatite composite materials property, in bone repair tissue engineering rack field, there is very high clinical value.
Summary of the invention
The object of the present invention is to provide a kind of Bacterial cellulose/collagen/hydroxyapatite composite and preparation method thereof.The present invention adopts the Bacterial cellulose thin film of porous after drying as matrix, by the capillary force action of its internal void and utilize ultrasonic accessory molecule diffusion method to impel collagen to be uniformly distributed in the network structure of bacteria cellulose fibre thin film, then the procyanidin of take is compound as cross-linking agent is cross-linked collagen under the condition of sonic oscillation, and the material after compound is processed and prepared Bacterial cellulose/collagen/hydroxyapatite composite by biomimetic mineralization.Composite of the present invention not only has unique bionic three-dimensional nanometer network structure and good mechanical property, and due to the introducing of collagen and hydroxyapatite, makes material more meet real structure and the composition of skeleton.Composite of the present invention has good biocompatibility, is conducive to adhesion, the Growth and reproduction of cell, is expected to meet the application requirements of bone tissue engineering stent material.Preparation technology of the present invention is simple, does not use any poisonous medicine, with low cost.
A kind of Bacterial cellulose/collagen/hydroxyapatite composite provided by the invention, by the capillary force action of Bacterial cellulose internal void and utilize ultrasonic auxiliary tropocollagen molecule diffusion method, with Bacterial cellulose dry film, collagen, procyanidin, CaCl
2with simulated body fluid be that raw material is made, Bacterial cellulose dry film, collagen, procyanidin, CaCl
2mass ratio be 10～200:1～50:4～6:6～10.
The preparation method of Bacterial cellulose/collagen/hydroxyapatite composite of the present invention, comprises the following steps:
Step 1, bacteria cellulose film is made after lyophilization to Bacterial cellulose dry film;
Step 2, collagen is joined in the acetic acid solution that concentration is 0.1～0.5M, be configured to the acetic acid solution that collagen concentration is 1～50g/l;
Step 3, the Bacterial cellulose dry film of making is immersed in the acetic acid solution that above-mentioned collagen concentration is 1～50g/L, then is placed in the ultrasonic 8～12h of ultrasonic washing instrument that power is 100～500W;
Step 4, the product that step 3 is obtained are put in the procyanidin solution that concentration is 4～6g/L, and control Bacterial cellulose dry film: collagen: the mass ratio of procyanidin is 10～200:1～50:4～6; Then ultrasonic 1～5h in the ultrasonic washing instrument of 100～500W, obtains cross-linking products;
Step 5, the cross-linking products that step 4 is obtained are put into the CaCl of 0.05～0.2mol/L
2solution, 37 ℃ of constant temperature soak 1～5 day, and every 24h changes a CaCl
2solution, obtains the gel film after pre-calcification;
Step 6, the gel film after pre-calcification obtaining in step 5 is put into the simulated body fluid preparing in advance, 37 ℃ of constant temperature soak 1～10d, and every 24h upgrades a simulated body fluid, obtains Bacterial cellulose/collagen/hydroxyapatite composite.
The present invention is first by the capillary force action of its internal void and utilize ultrasonic accessory molecule diffusion method, and with procyanidin as cross-linking agent, Bacterial cellulose dry film and collagen are carried out compound, collagen is uniformly distributed in the network of fibers of Bacterial cellulose, then by biomimetic mineralization, processes and prepare Bacterial cellulose/collagen/hydroxyapatite composite.The introducing of hydroxyapatite and collagen has not only improved the mechanical property of collagen itself, and also improved the biocompatibility of Bacterial cellulose itself, composite have unique three-dimensional manometer network structure and with the similar constituent feature of skeleton, this will be conducive to the breeding that grows in of osteocyte, is expected to meet the application requirements of bone tissue engineering stent material.
The present invention can complete the preparation of material under normal pressure, its technique is simple, and composite of the present invention has good biocompatibility, the adhesion, the growth and reproduction that with respect to single bacteria cellulose material, are more conducive to osteocyte, significant with application for the development of bone tissue engineering stent material.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of Bacterial cellulose/collagen/hydroxyapatite composite prepared in the embodiment of the present invention 1;
Fig. 2 is the stereoscan photograph of Bacterial cellulose/collagen prepared in the embodiment of the present invention 1;
Fig. 3 is the stereoscan photograph of Bacterial cellulose/collagen/hydroxyapatite composite prepared in the embodiment of the present invention 1.
The specific embodiment
Tell about by the following examples detailed process of the present invention, it is the convenience in order to understand that embodiment is provided, and is never restriction the present invention.
Embodiment 1:
According to following process, prepare Bacterial cellulose:
First, 12.5g glucose, 3.75g peptone, 5.00g yeast powder and 5.00g sodium hydrogen phosphate are dissolved in the beaker of the distilled water that is contained with 500ml, with glacial acetic acid, regulate pH to 4.5, liquid is poured in conical flask, sterilizing 0.5h under 115 ℃ of high temperature, as fluid medium.
With inoculating loop, get a ring acetobacter xylinum, be linked in the aforesaid liquid culture medium of 100ml, with gauze, tighten bottleneck, as for cultivating in shaking table, at 30 ℃, shake 30 hours, obtain acetobacter xylinum seed solution.
Acetobacter xylinum seed solution is no less than to 6% inoculum concentration according to percent by volume and is inoculated in the fluid medium after sterilizing, fully vibration makes bacterium liquid even, and the 30 ℃ of standing cultivation of constant temperature 5d, obtain bacterial cellulose gel film.With the sodium hydroxide solution of mass percent 1%, clean to milky, then be washed till neutrality with deionized water, so far obtain bacteria cellulose film.
According to following step, prepare Bacterial cellulose/collagen/hydroxyapatite composite of the present invention
First bacteria cellulose film is carried out to the Bacterial cellulose that lyophilization obtains dry state.
0.2g collagen is dissolved in the acetic acid solution that 100ml concentration is 0.1M.Get 2g Bacterial cellulose dry film and put into the acetic acid solution of this collagen, then being placed in power is the ultrasonic washing instrument sonic oscillation 8h of 300W, bacteria cellulose film is taken out, and putting into 100ml concentration is 5g/L procyanidin aqueous solution, then is placed in the ultrasonic washing instrument sonic oscillation 4h of 200W.After reaction finishes, gel film is put into the CaCl that 50ml concentration is 0.1mol/L
2in solution, 37 ℃ of constant temperature soak 3 days, during every day change CaCl one time
2solution.Gel film is taken out, be placed in the simulated body fluid that 50ml prepares in advance, at 37 ℃ of constant temperature, soak 5 days, obtain Bacterial cellulose/collagen/hydroxyapatite composite.
Preparation simulated body fluid: add successively NaCl, NaHCO in deionized water
3, KCl, K
2hPO
43H
2o and MgCl
26H
2o, joins to such an extent that the example concentration of simulated body fluid is 142.0mmol/L Na
+, 5.0mmol/L K
+, 3.8mmol/L Ca
2+, 1.5mmol/L Mg
2+, 6.3mmol/L HCO
3-, 148.5mmol/L Cl
-, 1.5mmol/L HPO
4 2-, 0.5mmol/L SO
4 2-, finally with Tris, pH value is adjusted to 7.4.
The present invention has successfully prepared Bacterial cellulose/collagen/hydroxyapatite composite first.There is the X-ray diffraction shown in Fig. 1 known, in material, occurred respectively the diffraction maximum of Bacterial cellulose, collagen and hydroxyapatite, and without the assorted peak of other materials, prove and make Bacterial cellulose/collagen/hydroxyapatite composite that composition is pure.
The present invention be take Bacterial cellulose dry film as matrix, utilize ultrasonic accessory molecule diffusion method to using procyanidin as cross-linking agent, first make Bacterial cellulose/collagen composite materials, collagen is in the nanometer network structure that irregular form is uniformly distributed in Bacterial cellulose, sees Fig. 2.Then again Bacterial cellulose/collagen composite materials is carried out to biomimetic mineralization processing, the nanofiber surface deposition hydroxyapatite at this composite, obtains Bacterial cellulose/collagen/hydroxyapatite composite.As shown in Figure 3, hydroxyapatite is evenly wrapped in fiber surface, and has still retained the good three-dimensional manometer network structure of Bacterial cellulose.
Embodiment 2:
0.1g collagen is dissolved in the acetic acid solution that 100ml concentration is 0.25M, 2g Bacterial cellulose dry film is put into the acetic acid solution of this collagen, then being placed in power is the ultrasonic washing instrument sonic oscillation 10h of 500W, take out bacteria cellulose film and put into the procyanidin aqueous solution that 100ml concentration is 4g/L, after sonic oscillation 4h, then this gel film is placed in to the CaCl that 50ml concentration is 0.2mol/L
2solution, soaks 2d, during every day change CaCl one time
2solution, obtains the gel film after pre-calcification.Then again this gel film is put into the simulated body fluid constant temperature preparing in advance and soaked 7d, obtain Bacterial cellulose/collagen/hydroxyapatite composite.Other experiment conditions are with EXPERIMENTAL EXAMPLE 1.
Although in conjunction with figure, invention has been described above; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment is only schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; in the situation that not departing from aim of the present invention, can also make a lot of distortion, within these all belong to protection scope of the present invention.
Claims (5)
1. Bacterial cellulose/collagen/hydroxyapatite composite, is characterized in that, by the capillary force action of Bacterial cellulose internal void and utilize ultrasonic auxiliary tropocollagen molecule diffusion method, with Bacterial cellulose dry film, collagen, procyanidin, CaCl
2with simulated body fluid be that raw material is made, Bacterial cellulose dry film, collagen, procyanidin, CaCl
2mass ratio be 10～200:1～50:4～6:6～10.
2. according to the composite of Bacterial cellulose/collagen/hydroxyapatite described in claim 1, it is characterized in that described all kinds of inorganic salt composition of simulated body fluid ion concentration is: 142.0mmol/L Na
+, 5.0mmol/L K
+, 3.8mmol/L Ca
2+, 1.5mmol/L Mg
2+, 6.3mmol/L HCO
3-, 148.5mmol/L Cl
-, 1.5mmol/L HPO
4 2-, 0.5mmol/L SO
4 2-.
3. a preparation method for Bacterial cellulose/collagen/hydroxyapatite composite as claimed in claim 1, is characterized in that, comprises the following steps:
Step 1, bacteria cellulose film is made after lyophilization to Bacterial cellulose dry film;
Step 2, collagen is joined in the acetic acid solution that concentration is 0.1～0.5M, be configured to the acetic acid solution that collagen concentration is 1～50g/l;
Step 3, the Bacterial cellulose dry film of making is immersed in the acetic acid solution that above-mentioned collagen concentration is 1～50g/L, then is placed in the ultrasonic 8～12h of ultrasonic washing instrument that power is 100～500W;
Step 4, the product that step 3 is obtained are put in the procyanidin solution that concentration is 4～6g/L, and control Bacterial cellulose dry film: collagen: the mass ratio of procyanidin is 10～200:1～50:4～6; Then ultrasonic 1～5h in the ultrasonic washing instrument of 100～500W, obtains cross-linking products;
Step 5, the cross-linking products that step 4 is obtained are put into the CaCl of 0.05～0.2mol/L
2solution, 37 ℃ of constant temperature soak 1～5 day, and every 24h changes a CaCl
2solution, obtains the gel film after pre-calcification;
Step 6, the gel film after pre-calcification obtaining in step 5 is put into the simulated body fluid preparing in advance, 37 ℃ of constant temperature soak 1～10d, and every 24h upgrades a simulated body fluid, obtains Bacterial cellulose/collagen/hydroxyapatite composite.
4. according to the preparation method of the composite of Bacterial cellulose/collagen/hydroxyapatite described in claim 3, wherein, all kinds of inorganic salt composition of described simulated body fluid ion concentration is: 142.0mmol/L Na
+, 5.0mmol/L K
+, 3.8mmol/L Ca
2+, 1.5mmol/L Mg
2+, 6.3mmol/L HCO
3-, 148.5mmol/L Cl
-, 1.5mmol/L HPO
4 2-, 0.5mmol/L SO
4 2-.
5. fungin/collagen/hydroxyapatite composite is applied to bone tissue engineering stent material.
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| CN107115565A (en) * | 2017-06-28 | 2017-09-01 | 陕西师范大学 | A kind of hydroxyapatite/phase in version lysozyme coating hybrid material and preparation method thereof |
| CN107473194A (en) * | 2017-10-10 | 2017-12-15 | 周益铭 | A kind of preparation method of nanometer hydroxyapatite |
| CN108888806A (en) * | 2018-08-06 | 2018-11-27 | 华中农业大学 | Osteoinductive material and its preparation method and application based on fish skin collagen aggregation |
| CN112402289A (en) * | 2020-10-26 | 2021-02-26 | 杜明春 | Bionic collagen solution for skin surface and preparation method and use method thereof |
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Cited By (5)
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|---|---|---|---|---|
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Application publication date: 20140402 |