CN108392674B - Preparation method of high-bioactivity glass nanofiber scaffold - Google Patents
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Abstract
The invention belongs to the field of biological functional materials, and discloses a preparation method of a high-bioactivity glass nanofiber scaffold, which comprises the following steps: respectively carrying out chemical reaction on the pure bacterial cellulose film in ceric ammonium nitrate and ethylenediamine solutions to graft amino onto hydroxyl of the bacterial cellulose to obtain aminated modified bacterial cellulose, and freeze-drying to obtain an aminated bacterial cellulose block. And then, respectively depositing precursors containing calcium and silicon elements on the surfaces of the bacterial cellulose by using the aminated bacterial cellulose as a template through an ultrasonic method, and calcining to obtain the nano biological glass fiber scaffold. The nano-fiber glass bracket has a superfine nano-scale network structure and a huge specific surface area, can quickly induce the formation of hydroxyapatite in body fluid, and has very high biological activity. The method has the advantages of simple process, easy operation, low cost and the like, and has good application prospect.
Description
Technical Field
The invention relates to the field of biological functional materials, in particular to a preparation method of a high-bioactivity glass nanofiber scaffold.
Background
Today, people pay more and more attention to the research of life science, and the biological material science is taken as the cross frontier field of the life science and the material science, and plays an immeasurable role in the rehabilitation engineering of human beings. As a representative example of biological materials, bioactive glass has attracted attention as a class of glass materials that can repair, replace and regenerate body tissues and can bond with tissues (particularly bone tissues), and is one of the hot topics in the international material research field at present. So far, a great deal of research reports that bioglass with high specific surface area and porosity has higher bioactivity and good biomimetic mineralization performance, and after being soaked in Simulated Body Fluid (SBF) for a period of time, bone-like hydroxyapatite carbonate crystals can be generated on the surface of the bioglass, which is one of the most important standards for judging whether the material has bioactivity. At present, the preparation scale of the biological glass bracket at home and abroad is mainly concentrated in front of micropores and macropores, the prepared biological material has smaller specific surface area and lower biological activity, and the great demand of human tissue engineering on the biological glass material is difficult to meet.
The bacterial cellulose has a superfine three-dimensional network structure, has huge three-dimensional space outside the nano-fiber, is easy to contain water, alcohols, inorganic substances, organic matter precursors and other solutions or sol particles and the like, provides conditions for the deposition of a target object on the surface of the bacterial cellulose, has nanoscale pore size distribution and larger specific surface area, and is widely applied to the field of biological functional nano-materials. However, because the surface hydroxyl of the bacterial cellulose has low chemical activity and is difficult to be combined with cations and other components under general conditions, the method for performing amination modification on the bacterial cellulose is adopted, so that the chemical active sites of the bacterial cellulose are increased, and the binding capacity of the cellulose to the cations is greatly improved. The invention is characterized in that the superfine network structure of bacterial cellulose is used as an organic template, and after a bioglass precursor component containing calcium and silicon is deposited, the bioglass nano-fiber scaffold with the same superfine nano-network structure is obtained by calcination, so that the bioactivity of the glass scaffold is improved. The method provides a new path for preparing the inorganic bioglass nanofiber scaffold, and has certain practical significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a nano-glass fiber bracket with simple operation process, three-dimensional superfine network structure, high specific surface area and high biological activity, which can realize batch production and is green and environment-friendly and aims to improve the induction and combination capacity of cellulose nano-fibers to biological glass precursor components by performing amination modification on bacterial cellulose so as to prepare the nano-biological glass fiber bracket with the nano-network structure.
The technical scheme of the invention is as follows:
(1) shearing a bacterial cellulose film into blocks, soaking the blocks in 0.5-2 mol/L NaOH solution at 90 ℃ for 2-5 h, then washing the blocks to be neutral by using a large amount of deionized water, and freeze-drying the blocks in a freeze dryer to obtain bacterial cellulose blocks;
(2) putting the bacterial cellulose block into constant-temperature water introduced at 35 ℃, continuously introducing nitrogen to remove oxygen dissolved in the water, adding a ceric ammonium nitrate solution with the concentration of 0.1 mol/L for reaction for 15 min, then continuously dripping poly glycidyl methacrylate GMA for 30 min, washing the bacterial cellulose block with deionized water after reacting for 2h, washing the bacterial cellulose block with absolute ethyl alcohol, repeatedly washing the bacterial cellulose block to be neutral to obtain a white block, and then freeze-drying the white block; wherein 1 mol/L HNO is dissolved in the ammonium ceric nitrate solution3(ii) a Wherein the mass ratio of the bacterial cellulose to the ammonium ceric nitrate to the GMA is 1:20: 2;
(3) putting the white block obtained in the step (2) into ethylene diamine according to the mass ratio: 2, stirring for 2-5 h at 80 ℃, finally washing with deionized water, then washing with absolute ethyl alcohol, repeating the steps until the mixture is neutral, obtaining the aminated bacterial cellulose, and then carrying out freeze drying;
(4) adding 0.1-1 mol/L Ca (NO) into the aminated cellulose obtained in the step (3)3)2·4H2Performing ultrasonic treatment in an ethanol solution of O for 3 hours to obtain the amino bacterial cellulose subjected to pre-calcification treatment, wherein the calcium-containing solution is replaced every 1 hour; wherein the mass of the aminated bacterial cellulose block and Ca (NO)3)2The mass ratio of the solution is 1: 2000;
(6) (5) taking out the pre-calcified aminated bacterial cellulose block obtained in the step (4), directly putting the pre-calcified aminated bacterial cellulose block into a silicon-containing solution, continuously performing ultrasonic treatment for 3 hours, replacing the silicon-containing solution every 1 hour to maintain the concentration of silicon ions, continuously washing the pre-calcified aminated bacterial cellulose block with deionized water after the ultrasonic treatment is completed, and then performing freeze drying; wherein the mass ratio of the pre-calcified amination bacterial cellulose block to the siliceous solution is 1: 2000; and (3) heating and sintering the finally freeze-dried aminated bacterial cellulose block, and calcining at 600-800 ℃ for 1-3 h to obtain the bioactive nano glass bracket.
The silicon-containing solution in the step (5) is specifically: tetraethyl orthosilicate TEOS: absolute ethanol = 1: 40 and mixing.
Solvents adopted in the step of freeze drying in the step are tert-butyl alcohol, water or mixed solution thereof.
And (4) the heating rate in the step (6) is 5-20 ℃/min.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages of simple process, easy operation, low cost and low time consumption, and has good industrialization prospect.
2. According to the invention, through a sol-gel method of performing amination modification and ultrasonic treatment on bacterial cellulose, the induction and binding capacity of bioglass precursor components on bacterial cellulose nanofibers is improved, and the nanometer bioglass fiber scaffold with a 3D network structure is prepared. The prepared bioactive glass bracket has higher specific surface area with high porosity and high bioactivity.
Drawings
Fig. 1 is a schematic flow chart of the preparation of the high-bioactivity glass nano-fiber scaffold.
FIG. 2 is an SEM image of the aminated bacterial cellulose of the present invention after ultrasonication in example 1.
FIG. 3 is an FTIR chart of the aminated bacterial cellulose NBC and bacterial cellulose BC prepared in the examples.
Detailed description of the invention
The technical solution of the present invention will be described in detail by examples, but the present invention is not limited thereto.
Example 1
A preparation method of a high-bioactivity glass nanofiber scaffold comprises the following steps:
(1) shearing a bacterial cellulose film into blocks, soaking the blocks in 1 mol/L NaOH solution at 90 ℃ for 2h, then washing the blocks to be neutral by using a large amount of deionized water, and freeze-drying the blocks in a freeze dryer to obtain the bacterial cellulose blocks;
(2) putting the bacterial cellulose block into water with nitrogen introduced at 35 ℃, adding 0.1 mol/L ceric ammonium nitrate solution (dissolved in 1 mol/L HNO)3) Reacting for 15 min, then dripping poly Glycidyl Methacrylate (GMA) for 30 min, reacting for 2h, washing with deionized water and alcohol for multiple times to neutrality to obtain a white block, and then freeze-drying; wherein 1 mol/L HNO is dissolved in the ammonium ceric nitrate solution3(ii) a Wherein the mass ratio of the bacterial cellulose to the ammonium ceric nitrate to the GMA is 1:20: 2; (3) putting the white block obtained in the step (2) into ethylene diamine according to the mass ratio: 2, stirring for 2-5 h at 80 ℃, finally washing with deionized water, then washing with absolute ethyl alcohol, repeating the steps until the mixture is neutral, obtaining the aminated bacterial cellulose, and then carrying out freeze drying;
(4) adding 0.1 mol/L Ca (NO) into aminated cellulose3)2·4H2Performing ultrasonic treatment for 3 h in ethanol solution of O, wherein the calcium-containing solution is replaced every 1 h; wherein the mass of the aminated bacterial cellulose block and Ca (NO)3)2The mass ratio of the solution is 1: 2000;
(5) taking out the pre-calcified aminated bacterial cellulose block obtained in the step (4), directly putting the pre-calcified aminated bacterial cellulose block into a silicon-containing solution, continuously performing ultrasonic treatment for 3 hours, replacing the silicon-containing solution every 1 hour to maintain the concentration of silicon ions, continuously cleaning the pre-calcified aminated bacterial cellulose block with deionized water after the ultrasonic treatment is completed, and then performing freeze drying; wherein the mass ratio of the pre-calcified amination bacterial cellulose block to the siliceous solution is 1: 2000;
(6) and calcining the finally freeze-dried aminated bacterial cellulose block (CaSi/NBC) at 700 ℃ for 1h to obtain the bioactive nano glass scaffold (NBG).
Example 2
A preparation method of a high-bioactivity glass nanofiber scaffold comprises the following steps:
(1) shearing a bacterial cellulose film into blocks, soaking the blocks in 1 mol/L NaOH solution at 90 ℃ for 2h, then washing the blocks to be neutral by using a large amount of deionized water, and freeze-drying the blocks in a freeze dryer to obtain the bacterial cellulose blocks;
(2) putting the bacterial cellulose block into water with nitrogen introduced at 35 ℃, adding 0.1 mol/L ceric ammonium nitrate solution (dissolved in 1 mol/L HNO)3) Reacting for 15 min, then dripping poly Glycidyl Methacrylate (GMA) for 30 min, reacting for 2h, washing with deionized water and alcohol for multiple times to neutrality to obtain a white block, and then freeze-drying; wherein 1 mol/L HNO is dissolved in the ammonium ceric nitrate solution3(ii) a Wherein the mass ratio of the bacterial cellulose to the ammonium ceric nitrate to the GMA is 1:20: 2;
(3) putting the white block obtained in the step (2) into ethylene diamine according to the mass ratio: 2, stirring for 2-5 h at 80 ℃, finally washing with deionized water, then washing with absolute ethyl alcohol, repeating the steps until the mixture is neutral, obtaining the aminated bacterial cellulose, and then carrying out freeze drying;
(4) adding 0.2 mol/L Ca (NO) into aminated cellulose3)2·4H2Performing ultrasonic treatment for 3 h in ethanol solution of O, wherein the calcium-containing solution is replaced every 1 h; wherein the mass of the aminated bacterial cellulose block and Ca (NO)3)2The mass ratio of the solution is 1: 2000;
(5) taking out the pre-calcified aminated bacterial cellulose block obtained in the step (4), directly putting the pre-calcified aminated bacterial cellulose block into a silicon-containing solution, continuously performing ultrasonic treatment for 3 hours, replacing the silicon-containing solution every 1 hour to maintain the concentration of silicon ions, continuously cleaning the pre-calcified aminated bacterial cellulose block with deionized water after the ultrasonic treatment is completed, and then performing freeze drying; wherein the mass ratio of the pre-calcified amination bacterial cellulose block to the siliceous solution is 1: 2000;
(6) and calcining the amination bacterial cellulose block obtained after final freeze drying at 700 ℃ for 1h to obtain the bioactive nano glass bracket.
Example 3
A preparation method of a high-bioactivity glass nanofiber scaffold comprises the following steps:
(1) shearing a bacterial cellulose film into blocks, soaking the blocks in 1 mol/L NaOH solution at 90 ℃ for 2h, then washing the blocks to be neutral by using a large amount of deionized water, and freeze-drying the blocks in a freeze dryer to obtain the bacterial cellulose blocks;
(2) putting the bacterial cellulose block into water with nitrogen introduced at 35 ℃, adding 0.1 mol/L ceric ammonium nitrate solution (dissolved in 1 mol/L HNO)3) Reacting for 15 min, then dripping poly Glycidyl Methacrylate (GMA) for 30 min, reacting for 2h, washing with deionized water and alcohol for multiple times to neutrality to obtain a white block, and then freeze-drying; wherein 1 mol/L HNO is dissolved in the ammonium ceric nitrate solution3(ii) a Wherein the mass ratio of the bacterial cellulose to the ammonium ceric nitrate to the GMA is 1:20: 2;
(3) putting the white block obtained in the step (2) into ethylene diamine according to the mass ratio: 2, stirring for 2-5 h at 80 ℃, finally washing with deionized water, then washing with absolute ethyl alcohol, repeating the steps until the mixture is neutral, obtaining the aminated bacterial cellulose, and then carrying out freeze drying;
(4) adding 0.5 mol/L Ca (NO) into aminated cellulose3)2·4H2Performing ultrasonic treatment for 3 h in ethanol solution of O, wherein the calcium-containing solution is replaced every 1 h; wherein the mass of the aminated bacterial cellulose block and Ca (NO)3)2The mass ratio of the solution is 1: 2000;
(5) taking out the pre-calcified aminated bacterial cellulose block obtained in the step (4), directly putting the pre-calcified aminated bacterial cellulose block into a silicon-containing solution, continuously performing ultrasonic treatment for 3 hours, replacing the silicon-containing solution every 1 hour to maintain the concentration of silicon ions, continuously cleaning the pre-calcified aminated bacterial cellulose block with deionized water after the ultrasonic treatment is completed, and then performing freeze drying; wherein the mass ratio of the pre-calcified amination bacterial cellulose block to the siliceous solution is 1: 2000;
(6) and calcining the amination bacterial cellulose block obtained after final freeze drying at 700 ℃ for 1h to obtain the bioactive nano glass bracket.
Claims (4)
1. A preparation method of a high-bioactivity glass nanofiber scaffold is characterized by comprising the following steps: the method comprises the following steps:
(1) shearing a bacterial cellulose film into blocks, soaking the blocks in 0.5-2 mol/L NaOH solution at 90 ℃ for 2-5 h, then washing the blocks to be neutral by using a large amount of deionized water, and freeze-drying the blocks in a freeze dryer to obtain bacterial cellulose blocks;
(2) putting the bacterial cellulose block into constant-temperature water of 35 ℃, continuously introducing nitrogen to remove oxygen dissolved in the water, adding a ceric ammonium nitrate solution with the concentration of 0.1 mol/L for reaction for 15 min, then dripping polyglycidyl methacrylate GMA for 30 min, washing the bacterial cellulose block with deionized water after reacting for 2h, washing the bacterial cellulose block with absolute ethyl alcohol, repeatedly washing the bacterial cellulose block to be neutral to obtain a white block, and then freeze-drying the white block; wherein 1 mol/L HNO is dissolved in the ammonium ceric nitrate solution3(ii) a Wherein the mass ratio of the bacterial cellulose to the ammonium ceric nitrate to the GMA is 1:20: 2;
(3) putting the white block obtained in the step (2) into ethylene diamine according to the mass ratio: the method comprises the following steps of (1) preparing 125 mL of mixed solution with water =3:2, stirring for 2-5 h at 80 ℃, finally washing with deionized water and ethanol to be neutral, and freeze-drying to obtain an aminated bacterial cellulose template;
(4) adding 0.1-1 mol/L Ca (NO) into the aminated bacterial cellulose3)2·4H2Performing ultrasonic treatment in ethanol solution of O for 3 h, and replacing Ca (NO) every 1h3)2The solution is used for ensuring the concentration of calcium ions; wherein the mass of the aminated bacterial cellulose block and Ca (NO)3)2The mass ratio of the solution is 1: 2000;
(5) placing the pre-calcified aminated bacterial cellulose block into a silicon-containing solution, continuing to perform ultrasonic treatment for 3 hours, replacing the silicon-containing solution every 1 hour to maintain the concentration of silicon ions, continuing to perform deionized water cleaning after the ultrasonic treatment is completed, and then performing freeze drying;
(6) and (3) calcining the block obtained in the step (5) at 600-800 ℃ for 1-6 h, and removing the bacterial cellulose template to obtain the nano glass fiber support.
2. The method for preparing the glass nano fiber scaffold with high bioactivity according to claim 1, wherein the method comprises the following steps: the silicon-containing solution in the step (5) is specifically: tetraethyl orthosilicate TEOS: absolute ethanol = 1: 40 and mixing.
3. The method for preparing the glass nano fiber scaffold with high bioactivity according to claim 1, wherein the method comprises the following steps: the mass ratio of the pre-calcified aminated bacterial cellulose to the siliceous solution in the step (5) is 1: 2000.
4. The method for preparing the glass nano fiber scaffold with high bioactivity according to claim 1, wherein the method comprises the following steps: and (4) in the step (6), the heating rate of the calcination is 5-20 ℃/min.
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