CN112957525B - Nano-hydroxyapatite/silk fibroin/cellulose composite aerogel and preparation method thereof - Google Patents
Nano-hydroxyapatite/silk fibroin/cellulose composite aerogel and preparation method thereof Download PDFInfo
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Abstract
A nano-hydroxyapatite/silk fibroin/cellulose composite aerogel and a preparation method thereof relate to a composite aerogel and a preparation method thereof. The problem that the mechanical property of the existing cellulose aerogel is poor is solved. The composite aerogel has a reticular structure formed by interweaving silk fibroin and cellulose, and the surface of the cellulose is coated with nano hydroxyapatite. The method comprises the following steps: 1. dispersing nano hydroxyapatite in water; 2. dispersing cellulose in a sodium hydroxide/urea solution, adding a cross-linking agent, a nano hydroxyapatite dispersion solution and a silk fibroin solution into the cellulose solution, and stirring; heating to obtain composite hydrogel, soaking the composite hydrogel in water, and replacing with tert-butyl alcohol; and (4) freeze-drying to obtain the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel. The composite aerogel material has the advantages of increasing the apparent density of the aerogel, improving the integrity, improving the toughness and strength of the composite aerogel material and having better mechanical properties. The invention is used in the field of aerogels.
Description
Technical Field
The invention relates to the field of aerogels, in particular to a composite aerogel and a preparation method thereof.
Background
The aerogel is a high-dispersion solid nano material which is in a nano porous network structure formed by mutually aggregating colloidal particles or polymer molecules and is filled with gaseous dispersion media in nanopores. The aerogel material has excellent characteristics, such as large porosity, large specific surface area, low thermal conductivity, low electrical conductivity and the like, so that the aerogel material plays a significant role in the fields of mechanics, thermal, optics, electromagnetism, electrochemistry and the like. Aerogels can be classified into inorganic aerogels, organic aerogels, and inorganic/organic composite aerogels according to their composition. The inorganic/organic composite aerogel combines the advantages of inorganic aerogel and organic aerogel, and has wide application in the fields of medical treatment, chemical industry and the like.
Cellulose is a natural polymer which has the largest reserve quantity in the world, is nontoxic, can be regenerated and degraded. The cellulose distribution is very wide, wherein the most common cotton fiber contains nearly 100 percent of cellulose, 80 to 90 percent of hemp and 40 to 50 percent of wood and bamboo. In addition, straw, bagasse, etc. are sources of cellulose. The cellulose aerogel has the advantages of reproducibility of cellulose and good processing toughness of the porous structure of the aerogel, so that the development prospect of the cellulose aerogel is better than that of the traditional aerogel. Cellulose aerogels can be classified into natural cellulose aerogels, regenerated cellulose aerogels and cellulose derivative aerogels.
The existing cellulose aerogel has poor mechanical properties and cannot meet the requirements of some fields on the mechanical strength of the aerogel.
Disclosure of Invention
The invention aims to solve the problem of poor mechanical properties of the existing cellulose aerogel and provides a nano hydroxyapatite/silk fibroin/cellulose composite aerogel and a preparation method thereof.
The nano hydroxyapatite/silk fibroin/cellulose composite aerogel has a mesh structure formed by interweaving silk fibroin and cellulose, and the surface of the cellulose is coated with the nano hydroxyapatite.
Furthermore, the nano hydroxyapatite is spherical and has the diameter of 50-150 nm.
The preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel comprises the following steps:
1. preparation of hydroxyapatite dispersion:
dispersing nano hydroxyapatite in deionized water, and performing ultrasonic treatment for 30-60 min to prepare uniformly dispersed nano hydroxyapatite dispersion; wherein the mass percentage concentration of the nano-hydroxyapatite in the nano-hydroxyapatite dispersion liquid is 10 to 20 percent;
2. preparing nano hydroxyapatite/silk fibroin/cellulose composite aerogel:
dispersing cellulose in a precooled sodium hydroxide/urea solution, and stirring for 5-10 min to obtain a uniform cellulose solution; the mass concentration of the cellulose solution is 0.1-1%;
adding a cross-linking agent, nano hydroxyapatite dispersion liquid and silk fibroin solution into the cellulose solution in sequence, and continuously stirring until a uniform dispersion system is formed;
then heating to 25-80 ℃, preserving the heat for 2-8 h to obtain crosslinked nano hydroxyapatite/silk fibroin/cellulose composite hydrogel, soaking and washing the composite hydrogel with deionized water to be neutral, and then replacing with tert-butyl alcohol; and (3) freezing the replaced composite hydrogel at-50 ℃ for 4-6 h, and then carrying out vacuum freeze drying for 24-36 h to obtain the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel.
Further, in the second step, the mass ratio of the cellulose to the hydroxyapatite to the silk fibroin is (6-8): (1-2): (1-2).
Further, in the second step, the mass ratio of sodium hydroxide, urea and water in the sodium hydroxide/urea solution is 7.
Further, in the second step, the cross-linking agent is epichlorohydrin.
Furthermore, the pre-cooling temperature in the step two is-12 to-15 ℃, and the pre-cooling time is 30 to 60min.
The preparation method of the nano hydroxyapatite in the first step comprises the following steps:
selecting polyacrylic acid as a stabilizer, adding water to swell for 12-48 h, and then adding CaCl 2 Stirring at constant temperature of 25-90 ℃ until the mixture is dissolved, adjusting the pH value to 10 by using sodium hydroxide solution, and then dropwise adding Na 2 HPO 4 Keeping the pH value of the system at 10, stirring for 2-3 h at 200-800 r/min, aging at room temperature for 1-2 days, centrifuging the obtained mixture at high speed, and washing the precipitate with absolute ethanol and water in sequenceWashing, and finally, freeze drying and high-temperature calcining to obtain the nano hydroxyapatite. CaCl 2 Ca and Na are neutralized 2 HPO 4 The molar ratio of P in (1.67).
Preferably, the centrifugal speed is 6000 to 8000r/min, and the centrifugal time is 10 to 30min.
Preferably, the calcination temperature is 800 to 1000 ℃.
Further, the preparation method of the fibroin solution in the second step comprises the following steps:
adding silk fibroin into a NaOH/urea mixed solution, and stirring at 20-60 ℃ until the silk fibroin is completely dissolved to obtain a silk fibroin solution, wherein the mass concentration of the silk fibroin solution is 1-5%; (ii) a Wherein the concentration of NaOH in the NaOH/urea mixed solution is 0.6-1.4 mol/L, and the concentration of urea is 8mol/L.
The invention has the beneficial effects that:
the hydroxyapatite has good environmental compatibility and biological activity, and compared with the common hydroxyapatite, the nano hydroxyapatite has more excellent physical and chemical properties: such as high solubility, large surface energy, better biological activity, etc.
Silk fibroin extracted from silk and spider silk is a natural structural protein. The silk fibroin is composed of 18 amino acids, has good biocompatibility, can be slowly degraded in vivo through hydrolysis, has no toxic or side effect on degradation products, and has nutrition and repair effects on surrounding tissues. Meanwhile, the surface of the silk fibroin has various chemical groups, so that the adhesion site is easy to be chemically and covalently modified.
The composite aerogel prepared from nano hydroxyapatite, silk fibroin and cellulose has good mechanical properties and biocompatibility.
1. In the composite aerogel, the nano-hydroxyapatite and the cellulose have good interface acting force, and the nano-hydroxyapatite can be uniformly dispersed on the surface of the cellulose to wrap the cellulose, so that the rigidity of the cellulose is improved. The nanometer hydroxyapatite is combined with the silk fibroin by the charge effect, and the nanometer hydroxyapatite can not completely coat the protein.
In the composite aerogel, the silk fibroin and the cellulose have good interface acting force, the silk fibroin and the cellulose with the surface coated with the nano-hydroxyapatite form a network structure, the apparent density of the cellulose aerogel is increased, the composite aerogel has better integrity, the toughness and the strength of the composite aerogel material are improved, the composite aerogel has better mechanical property, the tensile strength can reach 8-10 MPa, and the bending strength can reach 25-30 MPa.
2. The hydroxyapatite raw material, the silk fibroin and the cellulose adopted by the invention have low cost, excellent biocompatibility and environmental friendliness. The composite aerogel disclosed by the invention is degradable and is an environment-friendly composite material.
The composite aerogel prepared by the invention is suitable for bone tissue engineering application.
Drawings
Fig. 1 is a scanning electron microscope photograph (x 500) of the nano hydroxyapatite/silk fibroin/cellulose composite aerogel prepared in example 1;
fig. 2 is a scanning electron microscope photograph (x 1000) of the nano hydroxyapatite/silk fibroin/cellulose composite aerogel prepared in example 1;
fig. 3 is a scanning electron microscope photograph of the nano-hydroxyapatite/cellulose composite aerogel prepared in comparative example 1:
fig. 4 is a scanning electron microscope photograph of the silk fibroin/cellulose composite aerogel prepared in comparative example 2.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention discloses a nano hydroxyapatite/silk fibroin/cellulose composite aerogel, which has a net structure formed by interweaving silk fibroin and cellulose, wherein the surface of the cellulose is coated with nano hydroxyapatite.
Furthermore, the nano hydroxyapatite is spherical, and the diameter of the nano hydroxyapatite is 50-150 nm.
Spherical nano hydroxyapatite with the diameter of 50-150 nm is coated on the surface of the cellulose aerogel, so that the apparent density of the cellulose aerogel is increased, and the strength of the composite aerogel material is improved. In addition, the network structure formed by the silk fibroin and the cellulose enables the composite aerogel to have more integrity, and the toughness of the composite aerogel material is improved. The adopted hydroxyapatite, silk fibroin and cellulose raw materials have excellent biocompatibility, so that the prepared composite aerogel is suitable for bone tissue engineering application.
The preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel comprises the following steps:
1. preparation of hydroxyapatite dispersion:
dispersing nano hydroxyapatite in deionized water, and performing ultrasonic treatment for 30-60 min to prepare uniformly dispersed nano hydroxyapatite dispersion; wherein the mass percentage concentration of the nano-hydroxyapatite in the nano-hydroxyapatite dispersion liquid is 10 to 20 percent;
2. preparing nano hydroxyapatite/silk fibroin/cellulose composite aerogel:
dispersing cellulose in a precooled sodium hydroxide/urea solution, and stirring for 5-10 min to obtain a uniform cellulose solution; the mass concentration of the cellulose solution is 0.1-1%;
adding a cross-linking agent, nano hydroxyapatite dispersion liquid and silk fibroin solution into the cellulose solution in sequence, and continuously stirring until a uniform dispersion system is formed;
then heating to 25-80 ℃, preserving the heat for 2-8 h to obtain crosslinked nano hydroxyapatite/silk fibroin/cellulose composite hydrogel, soaking and washing the composite hydrogel with deionized water to be neutral, and then replacing with tert-butyl alcohol; and (3) freezing the replaced composite hydrogel at-50 ℃ for 4-6 h, and then carrying out vacuum freeze-drying for 24-36 h to obtain the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel.
The tertiary butanol is used for replacement to remove water in the composite hydrogel, and the specific operation method is to soak the composite hydrogel with the tertiary butanol and then repeatedly replace new tertiary butanol until the water is replaced.
Preferably, in the second step, the cross-linking agent, the nano-hydroxyapatite dispersion solution and the silk fibroin solution are sequentially added into the cellulose solution, wherein the mass ratio of the cellulose in the cellulose solution, the hydroxyapatite in the nano-hydroxyapatite dispersion solution and the silk fibroin in the silk fibroin solution is (6-8): (1-2): (1-2).
Preferably, the mass ratio of the sodium hydroxide, the urea and the water in the sodium hydroxide/urea solution in the second step is 7.
Preferably, in the second step, the crosslinking agent is epichlorohydrin.
Preferably, the pre-cooling temperature in the second step is-12 to-15 ℃, and the pre-cooling time is 30 to 60min.
As a preferred embodiment, the preparation method of the nano-hydroxyapatite in the first step comprises the following steps:
selecting polyacrylic acid as a stabilizer, adding water to swell for 12-48 h, and then adding CaCl 2 Stirring at constant temperature of 25-90 ℃ until the mixture is dissolved, adjusting the pH value to 10 by using sodium hydroxide solution, and then dropwise adding Na 2 HPO 4 Keeping the pH value of the system to be 10 all the time, stirring for 2-3 h at 200-800 r/min, aging at room temperature for 1-2 days, centrifuging the obtained mixture at high speed, washing the precipitate with absolute ethyl alcohol and water in sequence, and finally performing freeze drying and high-temperature calcination to obtain the nano-hydroxyapatite. CaCl 2 Ca and Na are neutralized 2 HPO 4 The molar ratio of P in (1.67).
Preferably, the centrifugal speed is 6000 to 8000r/min, and the centrifugal time is 10 to 30min.
Preferably, the calcination temperature is 800 to 1000 ℃.
As a preferred embodiment, the preparation method of the fibroin solution in the second step is as follows:
adding silk fibroin into a NaOH/urea mixed solution, and stirring at 20-60 ℃ until the silk fibroin is completely dissolved to obtain a silk fibroin solution, wherein the mass concentration of the silk fibroin solution is 1-5%; (ii) a Wherein the concentration of NaOH in the NaOH/urea mixed solution is 0.6-1.4 mol/L, and the concentration of urea is 8mol/L.
The technical scheme of the invention is further explained in detail by combining the specific embodiment and referring to the attached drawings.
Example 1:
the preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel comprises the following steps:
1. preparation of hydroxyapatite dispersion:
swelling 5g polyacrylic acid with 500ml water for 24h, and adding 2.77g CaCl 2 Stirring at 90 deg.C until dissolved, adjusting pH to 10 with sodium hydroxide solution, and mixing 500ml of 0.03mol/L Na at a ratio of n (Ca):n (P) =1.67 2 HPO 4 And dropwise adding the solution into the solution, dropwise adding a sodium hydroxide solution in the process to keep the pH =10 of the system, continuously stirring for 2h at 90 ℃, aging for 2 days at room temperature, centrifuging the obtained reaction mixture for 10min at 8000r/min, sequentially washing the precipitate with absolute ethyl alcohol and water, and finally freeze-drying and calcining at 800 ℃ to obtain the hydroxyapatite nanocrystal. Dispersing the prepared nano hydroxyapatite in deionized water, and performing ultrasonic dispersion for 30min to prepare uniformly dispersed hydroxyapatite dispersion.
2. Preparation of silk fibroin solution:
weighing 2.5g of silk fibroin, adding the silk fibroin into a NaOH/urea mixed solution, wherein the concentration of NaOH in the NaOH/urea mixed solution is 1.2mol/L of NaOH, the concentration of urea is 8mol/L, and stirring at 40 ℃ until the silk fibroin is completely dissolved to obtain the silk fibroin solution.
3. Preparing nano hydroxyapatite/silk fibroin/cellulose composite aerogel:
dispersing 7.5g of cellulose in a sodium hydroxide/urea solution (wherein the mass ratio of sodium hydroxide, urea and water is 7.
And (3) slowly adding a cross-linking agent epichlorohydrin, the nano-hydroxyapatite solution prepared in the first step and the silk fibroin solution prepared in the second step into the cellulose solution in sequence, and continuously stirring for 10min at-12 ℃ until a uniform dispersion system is formed.
And then heating to 25 ℃, preserving the temperature for 6 hours to obtain the crosslinked nano-hydroxyapatite/cellulose composite hydrogel, repeatedly soaking and washing with deionized water until the hydrogel is neutral, and then replacing with tert-butyl alcohol (namely repeatedly soaking with tert-butyl alcohol to replace the water therein). And (3) freeze-drying the replaced composite hydrogel at-50 ℃ for 24 hours to obtain the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel.
Scanning electron micrographs of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel prepared in this example are shown in fig. 1 and 2. As can be seen from the figure, the spherical nano-hydroxyapatite Dan Junyun is coated on the surface of the cellulose aerogel, and the silk fibroin and the cellulose coated with the nano-hydroxyapatite form a double-network structure. The nano hydroxyapatite/silk fibroin/cellulose composite aerogel is subjected to compression molding by die steel to test the mechanical property, the tensile strength is 10MPa, the bending strength is 30MPa, the mechanical property is excellent, and the requirements of bone tissue engineering application are met.
Comparative example 1:
the preparation method of the nano hydroxyapatite/cellulose composite aerogel in the comparative example comprises the following steps:
1. preparation of hydroxyapatite dispersion: 5g polyacrylic acid was swollen with 500ml water for 24h. 2.77g of CaCl are added 2 Stirring at 90 deg.C until dissolved, adjusting pH to 10 with sodium hydroxide solution, and mixing 500ml of 0.03mol/L Na at a ratio of n (Ca):n (P) =1.67 2 HPO 4 And dropwise adding the solution into the solution, dropwise adding a sodium hydroxide solution in the process to keep the pH of the system to be =10, continuously stirring at 800r/min for 2h at 90 ℃, aging at room temperature for 2 days, centrifuging the obtained reaction mixture at 8000r/min for 10min, sequentially washing the precipitate with absolute ethyl alcohol and water, and finally freeze-drying and calcining at 800 ℃ to obtain the hydroxyapatite nanocrystal. Dispersing the prepared nano hydroxyapatite in deionized water, and performing ultrasonic dispersion for 30min to prepare uniformly dispersed hydroxyapatite dispersion.
2. Preparing nano hydroxyapatite/cellulose composite aerogel: 4g of cellulose was dispersed in a solution of sodium hydroxide/urea/water (mass ratio 7. And (3) slowly adding 8mL of crosslinking agent epichlorohydrin and the nano-hydroxyapatite solution prepared in the first step into the cellulose solution in sequence, and continuously stirring for 10min at-12 ℃ until a uniform dispersion system is formed. Obtaining the cross-linked nano hydroxyapatite/cellulose composite hydrogel at 25 ℃, repeatedly soaking and washing with deionized water until the hydrogel is neutral, and then replacing with tert-butyl alcohol. And (3) freeze-drying the replaced composite hydrogel at-50 ℃ for 24 hours to obtain the nano-hydroxyapatite/cellulose composite aerogel.
The scanning electron microscope photograph of the nano-hydroxyapatite/cellulose composite aerogel prepared in comparative example 1 is shown in fig. 3. The mechanical properties of the steel are tested after compression molding by die steel, the tensile strength is 6MPa, and the bending strength is 22MPa.
Comparative example 2:
the preparation method of the silk fibroin/cellulose composite aerogel comprises the following steps:
1. preparation of silk fibroin solution: weighing 2.5g of silk fibroin, adding the silk fibroin into a mixed solution of 1.2mol/L NaOH and 8mol/L urea, and stirring at 40 ℃ until the silk fibroin is completely dissolved to obtain a silk fibroin solution.
2. Preparing silk fibroin/cellulose composite aerogel: 4g of cellulose was dispersed in a solution of-12 ℃ sodium hydroxide/urea/water (mass ratio 7. And (3) sequentially and slowly adding the cross-linking agent epichlorohydrin and the silk fibroin solution prepared in the step one into the cellulose solution, and continuously stirring for 10min until a uniform dispersion system is formed. Obtaining the cross-linked silk fibroin/cellulose composite hydrogel at 25 ℃, repeatedly soaking and washing with deionized water until the hydrogel is neutral, and then replacing with tert-butyl alcohol. And (3) freeze-drying the replaced composite hydrogel at-50 ℃ for 24h to obtain the silk fibroin/cellulose composite aerogel.
The scanning electron microscope photograph of the silk fibroin/cellulose composite aerogel prepared in comparative example 2 is shown in fig. 4. As can be seen from the figure, the sheet-shaped silk fibroin and the reticular cellulose are connected with each other to form a double-network structure. The mechanical properties of the steel are tested after compression molding by die steel, the tensile strength is 5MPa, and the bending strength is 20MPa.
The comparison shows that the nano hydroxyapatite/silk fibroin/cellulose composite aerogel has more excellent mechanical properties.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the nano hydroxyapatite/silk fibroin/cellulose composite aerogel is characterized by comprising the following steps:
1. dispersing nano hydroxyapatite in deionized water, and carrying out ultrasonic treatment for 30 to 60min to prepare a uniformly dispersed nano hydroxyapatite dispersion liquid; wherein the mass percentage concentration of the nano-hydroxyapatite in the nano-hydroxyapatite dispersion liquid is 10-20%;
2. dispersing cellulose in a precooled sodium hydroxide/urea solution, and stirring for 5 to 10min to obtain a uniform cellulose solution; the mass concentration of the cellulose solution is 0.1-1%;
adding a cross-linking agent, nano hydroxyapatite dispersion liquid and silk fibroin solution into the cellulose solution in sequence, and continuously stirring until a uniform dispersion system is formed;
heating to 25-80 ℃, keeping the temperature for 2-8 hours to obtain a crosslinked nano hydroxyapatite/silk fibroin/cellulose composite hydrogel, soaking and washing the composite hydrogel with deionized water to be neutral, and then replacing with tert-butyl alcohol; freezing the replaced composite hydrogel at-50 ℃ for 4 to 6 hours, and then carrying out vacuum freeze drying for 24 to 36 hours to obtain the nano hydroxyapatite/silk fibroin/cellulose composite aerogel;
the composite aerogel has a net structure formed by interweaving silk fibroin and cellulose, wherein the surface of the cellulose is coated with nano hydroxyapatite which is spherical and has the diameter of 50-150 nm.
2. The method for preparing nano hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 1, wherein the mass ratio of cellulose, nano hydroxyapatite and silk fibroin in step two is (6~8): (1~2): (1~2).
3. The preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 1, wherein the mass ratio of sodium hydroxide, urea and water in the sodium hydroxide/urea solution in the second step is 7.
4. The preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 1, wherein the precooling temperature in the second step is-12 to-15 ℃, and the precooling time is 30 to 60min.
5. The method for preparing nano hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 1, which is characterized in that the method for preparing nano hydroxyapatite in the first step comprises the following steps:
selecting polyacrylic acid as a stabilizer, adding water to swell for 12-48 h, and then adding CaCl 2 Stirring at constant temperature of 25 to 90 ℃ until the mixture is dissolved, adjusting the pH value to 10 by using a sodium hydroxide solution, and then dropwise adding Na 2 HPO 4 Keeping the pH of the system at 10 all the time, stirring for 2-3 h at 200-800 r/min, aging at room temperature for 1~2 days, centrifuging the obtained mixture at high speed, washing the precipitate with absolute ethyl alcohol and water in sequence, and finally performing freeze drying and high-temperature calcination to obtain nano hydroxyapatite; caCl 2 Ca and Na are neutralized 2 HPO 4 The molar ratio of P in (1.67).
6. The preparation method of the nano hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 5, wherein the centrifugation speed is 6000 to 8000r/min, and the centrifugation time is 10 to 30min.
7. The preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 5, wherein the calcination temperature is 800 to 1000 ℃.
8. The preparation method of the nano-hydroxyapatite/silk fibroin/cellulose composite aerogel according to claim 1, wherein the preparation method of the silk fibroin solution in the second step is as follows:
adding silk fibroin into a NaOH/urea mixed solution, and stirring at 20-60 ℃ until the silk fibroin is completely dissolved to obtain a silk fibroin solution, wherein the mass concentration of the silk fibroin solution is 1-5%; wherein the concentration of NaOH in the NaOH/urea mixed solution is 0.6 to 1.4mol/L, and the concentration of urea is 8mol/L.
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