CN106565974B - Alginate/hydroxyapatite overlong nanowire composite hydrogel - Google Patents
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Abstract
The present invention relates to alginate/hydroxyapatite overlong nanowire composite hydrogels, including water soluble algae hydrochlorate and hydroxyapatite overlong nanowire.The present invention combines water soluble algae hydrochlorate and hydroxyapatite overlong nanowire for the first time, and it is that reinforcing material forms alginate/hydroxyapatite overlong nanowire composite hydrogel to finally obtain one kind using alginate hydrogel as matrix, hydroxyapatite overlong nanowire.Alginate/hydroxyapatite overlong nanowire composite hydrogel prepared by the present invention also has both the characteristic of preferable biocompatibility while with good mechanical property.
Description
Technical field
The present invention relates to a kind of alginate/hydroxyapatite overlong nanowire composite hydrogel, the composite hydrogel packets
Containing two kinds of components of alginate and hydroxyapatite overlong nanowire, there is the pore passage structure of connection and good mechanical property,
Belong to biomaterial preparation field.
Background technology
Bio-medical composition is the bio-medical material being combined by two or more different materials, it
It is mainly used for the structure of reparation, the replacement and artificial organs of tissue.Long-term clinical application finds that homogenous material generally cannot
Meet the requirement of clinical application well.It is not only simultaneous using bio-medical composition made of Material cladding of different nature
Have the property of component materials, and the new capability that one-component material does not have can be obtained, is similar to obtain structure and performance
The bio-medical material of tissue opens a wide approach, and bio-medical composition has become bio-medical material
An important research field in material research.
Alginate is one kind by two kinds of (Isosorbide-5-Nitrae)-beta-D-mannuronic acid (M) and (Isosorbide-5-Nitrae)-α-L- guluronic acids (G)
The linear natural polymer that structural unit is irregularly formed by connecting.When alginate and Ca2+It, can be with Ca when contact2+It is coordinated and wink
Between gelation formed with " egg shell " structure calcium alginate hydrogel, Gelation Conditions are mild, and have good biology
Compatibility, therefore have a good application prospect in biomedical sector.Hydroxyapatite, molecular formula Ca10(PO4)6(OH)2, it is
The important inorganic constituents of skeleton and tooth is formed, there is good biocompatibility and bioactivity, it can be strong with bon e formation
Chemical bonding.Under the action of body fluid, it may occur that gradually degradation releases calcium and phosphorus, and the utilization that is absorbed by the body, grows
New bone tissue, to generate bone conduction effect.But its intensity is low, poor toughness, limits it in carrying position Bone Defect Repari
Using.
Currently, the sodium alginate of document report/hydroxyapatite nanoparticle composite hydrogel, mechanical property are carried
Height, and there is good biocompatibility, but it still needs further improvement for its mechanical property.Researcher is preparing alginic acid brine
A large amount of research has been done in terms of gel, has been commonly ionic cross-linking at gluing method, when crosslinking is typically by alginate solution
Be added drop-wise in calcium salt soln, but obtained gel plastic rate is uncontrollable, and hardly result in good mechanical property, structure it is uniform,
Complex-shaped three-dimensional structure.
Invention content
In view of the above-mentioned problems, alginate is combined by the present invention with hydroxyapatite nano line for the first time, one kind is provided
Alginate with connected pore channel structure and excellent mechanical performances/hydroxyapatite overlong nanowire composite hydrogel.
On the one hand, the present invention provides a kind of alginate/hydroxyapatite overlong nanowire composite hydrogels, including water
Solubility alga hydrochlorate and hydroxyapatite overlong nanowire.The alginate/hydroxyapatite overlong nanowire compound water congealing
The hydroxyapatite overlength nanometer that glue specifically includes alginate hydrogel and is scattered in the alginate hydrogel
Line.
The present invention combines water soluble algae hydrochlorate and hydroxyapatite overlong nanowire for the first time, finally obtains one kind with seaweed
Hydrochlorate hydrogel is matrix, hydroxyapatite overlong nanowire is that reinforcing material formation alginate/hydroxyapatite overlength is received
Rice noodles composite hydrogel.Wherein the more common hydroxyapatite of hydroxyapatite overlong nanowire have better mechanical property and
Flexility can be tightly combined with calcium alginate hydrogel matrix, form the structure of " armored concrete " formula, be had
The hydrogel of excellent mechanical performances.In addition, hydroxyapatite overlong nanowire has good biocompatibility, it is prepared in this way
Alginate/hydroxyapatite overlong nanowire composite hydrogel while with good mechanical property, also have both compared with
The characteristic of good biocompatibility.
Preferably, the mass ratio of the hydroxyapatite overlong nanowire and alginate is 0.1%~70%.
Preferably, the length range of the hydroxyapatite overlong nanowire is 30 microns~1000 microns, nano wire
A diameter of 5 nanometers~100 nanometers.
Preferably, the composite hydrogel has the pore passage structure of connection, bore dia adjustable.The hydroxyapatite is super
The duct inner wall of long nano wire and composite hydrogel is combined closely.Therefore, " armored concrete " formula structure can be formed, is carried significantly
High compound water congealing glue material mechanical property.
On the other hand, the present invention also provides a kind of alginate/hydroxyapatite overlong nanowire composite hydrogels
Preparation method, including：
Water soluble algae acid salt aqueous solution and water-soluble calcium saline solution are prepared respectively；
Hydroxyapatite nano line and water soluble algae acid salt aqueous solution are uniformly mixed, mixing suspension is obtained；
After addition water-soluble calcium saline solution makes its gelation in mixing suspension in a manner of sprinkling, then immerse water-soluble
10 minutes~24 hours in property calcium salt soln, alginate/hydroxyapatite overlong nanowire composite hydrogel is obtained.
The present invention is using water soluble algae hydrochlorate as matrix, hydroxyapatite overlong nanowire as reinforcing material, He Shui
Dissolubility calcium salt is as crosslinking agent, and formed in situ prepares alginate/hydroxyapatite overlong nanowire composite hydrogel after mixing.
And control plastic rate by the way of spraying calcium saline solution droplet so that prepared compound water congealing plastic structure is uniform, has
There are the pore passage structure of connection and good mechanical property.
Preferably, the water soluble algae hydrochlorate be sodium alginate and/or its hydrate, and/or potassium alginate and/or its
Hydrate.
Also, preferably, the molar concentration of the water soluble algae acid salt aqueous solution is 0.01~10 mol/L.
Preferably, the water-soluble Ca salt is at least one of calcium chloride, calcium nitrate, calcium acetate.
Also, preferably, the molar concentration of the water-soluble calcium saline solution be 0.01~10 mol/L, preferably 0.1~
0.5 mol/L.
Preferably, the mass ratio of hydroxyapatite nano line and water soluble algae hydrochlorate is 1 in the mixing suspension:10
~10:1.
The invention has the advantages that：
Its ultimate tensile strength of composite hydrogel prepared by the present invention is 0.123-0.178MPa, and young's modulus in tension is
0.242-0.994MPa, greatest compressive strength 0.090-0.125MPa, Modulus of pressure E50%For 0.089-0.123MPa；
The three-dimensional communication bore dia of alginate provided by the invention/hydroxyapatite overlong nanowire composite hydrogel is
200~500 μm, there is good biocompatibility and mechanical property, be suitably applied the biologies such as medicament slow release, bone tissue reparation
Medical domain；
The preparation process of the present invention is simple and convenient to operate, the equipment for not needing complex and expensive, is expected to realize industrialization, tool
There is good application prospect.
Description of the drawings
Fig. 1 a-1b are scanning electron microscopy (SEM) figure for being hydroxyapatite overlong nanowire prepared by embodiment 1；
Fig. 2 a-2b are the scanning electron microscopy of alginate/hydroxyapatite overlong nanowire composite hydrogel prepared by the present invention
(SEM) figure.
Specific implementation mode
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is using the aqueous solution of alginate (for example, sodium alginate and/or potassium alginate etc.) as matrix, hydroxyl
Apatite overlong nanowire is reinforcing material, and hydroxyapatite overlong nanowire is evenly spread to alginic acid under stirring at room temperature
In saline solution, mixing suspension.Then using calcium ion be crosslinking agent by spray water-soluble calcium saline solution (in water-soluble calcium
In saline solution spraying) so that mixing suspension is gradually converted into alginate/hydroxyapatite overlong nanowire compound water congealing
Glue.
Alginate prepared by the present invention/hydroxyapatite overlong nanowire composite hydrogel includes alginate water-setting
Glue and the hydroxyapatite overlong nanowire being scattered in the alginate hydrogel.Wherein, the alginate/hydroxyl
In base apatite overlong nanowire composite hydrogel the mass percent of hydroxyapatite overlong nanowire can be 0.1%~
70%, preferably 5~30%.
Illustrate to following exemplary alginate provided by the invention/hydroxyapatite overlong nanowire composite hydrogel
Preparation method.
Solvent-thermal method preparation may be used in hydroxyapatite overlong nanowire of the present invention, can refer to document and patent report
It is prepared by the method in road：Zhu Yingjie, Lu Bingqiang, Chen Feng, the non-ignitable hydroxyapatite paper and preparation method thereof of high-flexibility high temperature resistant,
Patent No. ZL201310687363.2；Ying-Ying Jiang,Ying-Jie Zhu,Feng Chen,Jin Wu,Ceramics
International,41,6098-6102(2015)；Yong-Gang Zhang,Ying-Jie Zhu Feng Chen,Jin
Wu,Materials Letters,144,135-137(2015).Other suitable preparation methods can also be used, method therefor is only
It wants that the hydroxyapatite overlong nanowire can be prepared.
Water-soluble calcium saline solution and water soluble algae acid salt aqueous solution is respectively configured.Wherein, the water soluble algae acid
The molar concentration of saline solution can be 0.01~2 mol/L.The molar concentration of the water-soluble calcium saline solution can be 0.01~
5 mol/Ls, preferably its molar concentration are 0.1~0.5 mol/L.
Hydroxyapatite overlong nanowire and alginate aqueous solution are stirred at room temperature.The time being wherein stirred at room temperature
It it is -24 hours 10 minutes, preferably 10 minutes~10 hours, the further preferred time that is stirred at room temperature was 60~120 minutes.
The mixed liquor of alginate and hydroxyapatite overlong nanowire is transferred in the mold of definite shape, on it
Side's sprinkling water-soluble calcium saline solution, calcium ion are coordinated and gelation with alginate.
Mold and composite hydrogel therein are immersed in the water-soluble calcium saline solution of room temperature 10 points after gel forming
Clock~24 hour obtain alginate/hydroxyapatite overlong nanowire so that calcium ion is spread uniformly in composite hydrogel
Composite hydrogel.
In the present invention, the length range of the hydroxyapatite overlong nanowire can be 30 microns~1000 micron, nanometers
The diameter of line can be 5 nanometers~100 nanometers.
In the present invention, the water-soluble Ca salt include but is not limited to calcium chloride and/or its hydrate, calcium nitrate and/or
Its hydrate, calcium acetate and/or its hydrate.It should be understood that a kind of water-soluble Ca salt can be used, can also be used two kinds or two kinds with
On water-soluble Ca salt；In addition it should be further appreciated that using water-soluble Ca salt hydrate, such as CaCl2·2H2O。
In the present invention, it is described for water soluble algae hydrochlorate include but is not limited to sodium alginate and/or its hydrate, seaweed
Sour potassium and/or its hydrate, it should be understood that a kind of water soluble algae salt can be used, two or more water soluble algae acid can also be used
Salt.
Composite hydrogel of the present invention includes two kinds of components of alginate and hydroxyapatite overlong nanowire, the hydroxyl
The length range of base apatite overlong nanowire can be 30 microns~1000 microns, nano wire a diameter of 5 nanometers~100 is received
Rice.The alginate is sodium alginate and/or its hydrate, potassium alginate and/or its hydrate.Alginate/hydroxyl phosphorus
The weight percent of hydroxyapatite overlong nanowire is 0.1%~70% in lime stone overlong nanowire composite hydrogel.It is described
Alginate/hydroxyapatite overlong nanowire composite hydrogel has the pore passage structure of connection.In composite hydrogel, hydroxyl
Apatite overlong nanowire is combined closely with calcium alginate hydrogel inner wall, formed " armored concrete " formula structure (such as Fig. 2 a and
Shown in Fig. 2 b), substantially increase compound water congealing glue material mechanical property.Alginate selected by the present invention is widely present and nature
In, there is biological degradability, it is environmental-friendly；Hydroxyapatite is the main inorganic composition of vertebrate tooth and bone, is had good
Good biocompatibility, therefore alginate/hydroxyapatite overlong nanowire composite hydrogel is in multiple necks such as biomedicine
Domain has a good application prospect.
Alginate selected by the present invention is widely present and in nature, has biological degradability, environmental-friendly.Hydroxyl phosphorus
Lime stone is the main inorganic composition of vertebrate tooth and bone, has good biocompatibility, therefore alginate/hydroxyl phosphorus
Lime stone overlong nanowire composite hydrogel has a good application prospect in multiple fields such as biomedicines.The present invention is by hydroxyl phosphorus
Lime stone overlong nanowire is compound in alginate hydrogel, can significantly improve mechanical property and the life of alginate hydrogel
Object performance achievees the purpose that extend alginate hydrogel application range has weight to the application for extending alginate hydrogel
The scientific meaning and application value wanted.
The present invention obtains with good mechanics the humidification of basis material using hydroxyapatite overlong nanowire
The composite hydrogel of performance and biology performance.The present invention is also controlled by the way of spraying calcium saline solution droplet described compound
Hydrogel plastic rate so that prepared composite hydrogel has the pore passage structure of connection and good mechanical property.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
The preparation of 1 hydroxyapatite overlong nanowire of embodiment
At room temperature, respectively by 0.1760g CaCl2、0.3480g NaH2PO4, 0.700g NaOH be dissolved in 10mL deionizations
In water.30min will be mixed under 9mL deionized waters, 4mL methanol, 7mL oleic acid magnetic agitations, 10mL is added dropwise successively later
CaCl2Solution, 10mL NaOH solutions, 10mL NaH2PO4Solution continues to stir 30min.Then this mixed solution is transferred to
In 100mL reaction kettles, sealing, after 180 DEG C of reactions for 24 hours, cooled to room temperature, product precipitates in ethanol, then with water, ethyl alcohol
It is washed repeatedly with hexamethylene repeatedly, until hydroxyapatite overlong nanowire water slurry pH close to 7.4, is protected at 4 DEG C later
It deposits.Hydroxyapatite overlong nanowire is finally obtained, as seen in figure la and lb.
Embodiment 2 (pure calcium alginate hydrogel)
At room temperature, by 2.0000g CaCl2100 ml deionized waters are dissolved in, 0.2000g sodium alginates are dissolved in 10 millis
It rises in water, 90min is stirred at room temperature, sodium alginate is made fully to dissolve.Sodium alginate soln is transferred to the mould of definite shape later
In tool, water-soluble calcium salting liquid and gelation are sprayed above it, by mold and composite hydrogel therein after gel forming
Immerse 37 DEG C of CaCl212h in aqueous solution, so that calcium ion is spread uniformly in composite hydrogel.Pure calcium alginate hydrogel
Internal aperture is at 200~500 μm, and the inside aperture of pure calcium alginate hydrogel is connection.Its ultimate tensile strength is
0.086MPa, young's modulus in tension 0.162MPa, greatest compressive strength 0.061MPa, Modulus of pressure E50%For 0.075MPa.
Embodiment 3
At room temperature, by 2.0000g CaCl2100 ml deionized waters are dissolved in, 0.2000g sodium alginates are dissolved in 10 millis
In the deionized water for rising the overlong nanowire of hydroxyapatite containing 0.0400g, 90min is stirred at room temperature, sodium alginate is made fully to dissolve,
And it is uniformly mixed with hydroxyapatite overlong nanowire.Sodium alginate soln is transferred in the mold of definite shape later,
Its uppermost spray CaCl2Aqueous solution is allowed to gelation, and mold and composite hydrogel therein are immersed 37 DEG C after gel forming
CaCl212h in aqueous solution, so that calcium ion is spread uniformly in composite hydrogel.The alginate/hydroxyapatite overlength
The ultimate tensile strength of nano wire composite hydrogel is 0.137MPa, young's modulus in tension 0.253MPa, greatest compressive strength
For 0.090MPa, Modulus of pressure E50%For 0.089MPa.
Embodiment 4
At room temperature, by 2.0000g CaCl2100 ml deionized waters are dissolved in, 0.2000g sodium alginates are dissolved in 10 millis
In the deionized water for rising the overlong nanowire of hydroxyapatite containing 0.0667g, 90min is stirred at room temperature, sodium alginate is made fully to dissolve,
And it is uniformly mixed with hydroxyapatite overlong nanowire.Sodium alginate soln is transferred in the mold of definite shape later,
Its uppermost spray CaCl2Aqueous solution is allowed to gelation, and mold and composite hydrogel therein are immersed 37 DEG C after gel forming
CaCl212h in aqueous solution, so that calcium ion is spread uniformly in composite hydrogel.The alginate/hydroxyapatite overlength
The ultimate tensile strength of nano wire composite hydrogel is 0.123MPa, young's modulus in tension 0.242MPa, greatest compressive strength
For 0.111MPa, Modulus of pressure E50%For 0.106MPa.
Embodiment 5
At room temperature, by 2.0000g CaCl2100 ml deionized waters are dissolved in, 0.2000g sodium alginates are dissolved in 10 millis
In the deionized water for rising the overlong nanowire of hydroxyapatite containing 0.1000g, 90min is stirred at room temperature, sodium alginate is made fully to dissolve,
And it is uniformly mixed with hydroxyapatite overlong nanowire.Sodium alginate soln is transferred in the mold of definite shape later,
Its uppermost spray CaCl2Aqueous solution and be allowed to gelation, mold and composite hydrogel therein are immersed 37 after gel forming
DEG C CaCl212h in aqueous solution, so that calcium ion is spread uniformly in composite hydrogel.Alginate/the hydroxyapatite is super
The ultimate tensile strength of long nano wire composite hydrogel is 0.175MPa, young's modulus in tension 0.381MPa, and maximum compression is strong
Degree is 0.112MPa, Modulus of pressure E50%For 0.112MPa.
Embodiment 6
At room temperature, by 2.0000g CaCl2100 ml deionized waters are dissolved in, 0.2000g sodium alginates are dissolved in 10 millis
In the deionized water for rising the overlong nanowire of hydroxyapatite containing 0.2000g, 90min is stirred at room temperature, sodium alginate is made fully to dissolve,
And it is uniformly mixed with hydroxyapatite overlong nanowire.Sodium alginate soln is transferred in the mold of definite shape later,
Its uppermost spray CaCl2Aqueous solution is allowed to gelation, and mold and composite hydrogel therein are immersed 37 DEG C after gel forming
CaCl212h in aqueous solution, so that calcium ion is spread uniformly in composite hydrogel.The alginate/hydroxyapatite overlength
The ultimate tensile strength of nano wire composite hydrogel is 0.178MPa, young's modulus in tension 0.509MPa, greatest compressive strength
For 0.113MPa, Modulus of pressure E50%For 0.113MPa.
Embodiment 7
At room temperature, by 2.0000g CaCl2100 ml deionized waters are dissolved in, 0.2000g sodium alginates are dissolved in 10 millis
In the deionized water for rising the overlong nanowire of hydroxyapatite containing 0.4000g, 90min is stirred at room temperature, sodium alginate is made fully to dissolve,
And it is uniformly mixed with hydroxyapatite overlong nanowire.Sodium alginate soln is transferred in the mold of definite shape later,
Its uppermost spray CaCl2Aqueous solution is allowed to gelation, and mold and composite hydrogel therein are immersed 37 DEG C after gel forming
CaCl212h in aqueous solution, so that calcium ion is spread uniformly in composite hydrogel.The alginate/hydroxyapatite overlength
The ultimate tensile strength of nano wire composite hydrogel is 0.175MPa, young's modulus in tension 0.994MPa, greatest compressive strength
For 0.125MPa, Modulus of pressure E50%For 0.123MPa.
Industrial applicability：The preparation process letter of alginate of the present invention/hydroxyapatite overlong nanowire composite hydrogel
Equipment that is single, easy to operate, not needing complex and expensive, it is easy to accomplish industrialized production.Alginate/hydroxyl provided by the invention
Apatite overlong nanowire composite hydrogel has a good application prospect in multiple fields such as biomedicines.
Claims (10)
1. a kind of alginate/hydroxyapatite overlong nanowire composite hydrogel, which is characterized in that include water soluble algae acid
Salt and hydroxyapatite overlong nanowire, the length of the hydroxyapatite overlong nanowire is 30~1000 microns, a diameter of 5
~100 nanometers.
2. alginate according to claim 1/hydroxyapatite overlong nanowire composite hydrogel, which is characterized in that
The water soluble algae hydrochlorate is sodium alginate and/or its hydrate, and/or potassium alginate and/or its hydrate.
3. alginate according to claim 1/hydroxyapatite overlong nanowire composite hydrogel, which is characterized in that
The mass percent of hydroxyapatite overlong nanowire in the alginate/hydroxyapatite overlong nanowire composite hydrogel
It is 0.1%~70%.
4. alginate according to any one of claim 1-3/hydroxyapatite overlong nanowire composite hydrogel,
It is characterized in that, the composite hydrogel has the pore passage structure of connection, channel diameter adjustable.
5. a kind of alginate as described in any one of claim 1-4/hydroxyapatite overlong nanowire composite hydrogel
Preparation method, which is characterized in that including：
The evenly dispersed mixing suspension and water solubility for having water soluble algae hydrochlorate and hydroxyapatite nano line is prepared respectively
Calcium saline solution；
Water-soluble calcium saline solution is added in mixing suspension in a manner of spraying droplet, makes the mix suspending pension gelation
Afterwards, it then immerses in water-soluble calcium salting liquid 10 minutes~24 hours, it is compound to obtain alginate/hydroxyapatite overlong nanowire
Hydrogel.
6. preparation method according to claim 5, which is characterized in that in the mixing suspension, water soluble algae hydrochlorate
Molar concentration be 0.01~10 mol/L.
7. preparation method according to claim 5, which is characterized in that hydroxyapatite overlength is received in the mixing suspension
The mass ratio of rice noodles and water soluble algae hydrochlorate is 1:10~10:1.
8. preparation method according to claim 5, which is characterized in that the water-soluble Ca salt is calcium chloride, calcium nitrate, second
At least one of sour calcium.
9. according to the preparation method described in any one of claim 5-8, which is characterized in that the water-soluble calcium saline solution
Molar concentration is 0.01~10 mol/L.
10. preparation method according to claim 9, which is characterized in that the molar concentration of the water-soluble calcium saline solution
For 0.1~0.5 mol/L.
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| CN107892286B (en) * | 2017-11-07 | 2020-11-10 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite super-long nanowire aerogel |
| CN108030961A (en) * | 2017-12-04 | 2018-05-15 | 上海富吉医疗器械有限公司 | Medical injection material and its preparation method and application |
| CN109529110A (en) * | 2018-12-10 | 2019-03-29 | 上海摩漾生物科技有限公司 | Porous nano hydroxyapatite sustained-release gel preparation method |
| CN111195372B (en) * | 2020-01-16 | 2021-07-23 | 北京诺康达医药科技股份有限公司 | Porous bone repair material and preparation method thereof |
| CN113388151B (en) * | 2021-07-16 | 2023-03-17 | 浙江理工大学 | Preparation method of nano cellulose fiber-sodium alginate-hydroxyapatite flame-retardant aerogel |
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