CN104928908A - Method for mineralizing silk fiber - Google Patents
Method for mineralizing silk fiber Download PDFInfo
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- CN104928908A CN104928908A CN201510406788.0A CN201510406788A CN104928908A CN 104928908 A CN104928908 A CN 104928908A CN 201510406788 A CN201510406788 A CN 201510406788A CN 104928908 A CN104928908 A CN 104928908A
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- silk fiber
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- silk
- fiber
- aqueous solution
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Abstract
The invention discloses a method for mineralizing silk fiber. The method comprises the steps of adding stearyl amine into a mixed solution of linoleic acid and ethyl alcohol, stirring the mixed solution until the mixed solution is dissolved completely, adding a Ca(NO[3])[2] aqueous solution, standing the solution until the solution is layered, and adding a Na[3]PO[4] aqueous solution and stirring; adding the silk fiber, making the silk fiber is immersed by the solution, and heating the solution at a high temperature; taking out the silk fiber, washing the silk fiber with ethyl alcohol, removing the uncombined elements on the surface of the silk fiber, and achieving the mineralization of the silk fiber. According to the method, the superiority supplementary between the silk fiber and hydroxyapatite is achieved, on the basis of keeping the hydroxyapatite as bone tissue engineering materials, the mechanical properties of materials are improved, and the silk fiber/hydroxyapatite composite materials are biological materials of great properties and can be applied to bone tissue engineering widely.
Description
Technical field
The present invention relates to a kind of silk fiber processing method, especially relate to a kind of mineralization methods of silk fiber, belong to natural polymer field.
Background technology
Fibroin has good biocompatibility and mechanical strength, it is a kind of degradable biological macromolecular material, its catabolite has no side effect to cell or body, also seldom immunological rejection or inflammatory reaction is produced, utilize these advantages of silk-fibroin, silk-fibroin can be processed into porous support or membrane material, also can carry out biomineralization, obtain biomaterial of good performance.Silk-fibroin, as a kind of good cell growth medium, can promote the Growth and reproduction of cell, and the research of silk fibroin solution mineralising is very common, and not yet there is report the silk fiber mineralising world.
Summary of the invention
In order to solve problems of the prior art, the present invention proposes a kind of mineralization methods of silk fiber, the present invention is the process that synthesizing hydroxylapatite limit, a limit completes mineralising, utilize micro emulsion method synthesizing hydroxylapatite and add the common pyroreaction of silk fiber, make hydroxyapatite at fibroin fiber surface aggregation and be covered in fibroin fiber surface.The inventive method technique is simple, and processing ease, manufacturing cycle is short, good biocompatibility.
The technical solution used in the present invention comprises the following steps:
(1) stearylamine is joined in the linoleic acid that volume ratio is 1:2 ~ 6 and alcohol mixed solution, be stirred to and dissolve completely, add Ca (NO
3)
2after aqueous solution stratification, then add Na
3pO
4stir after the aqueous solution;
(2) added by silk fiber in the solution that step (1) obtains, in silk fiber and step (1), the mass ratio of solution is less than 1:10, makes solution submergence silk fiber, heats 6-12h under 100 DEG C of hot conditions;
(3) take out silk fiber in step (2), use ethanol purge silk fiber, remove the non-binding constituents on silk fiber surface, realize the mineralising of silk fiber.
Silk cellulose fiber after cleaning can be SEM and observe, to verify mineralising result by result.
Described Ca (NO
3)
2ca in the aqueous solution
2+and Na
3pO
4pO in the aqueous solution
4 3-the mol ratio 1.67 of ion.
The fibroin fiber that in described step (1), silk fiber comprises raw silk, degumming process is crossed or the silk fiber that method of plasma processing obtains.
In silk fiber/hydroxyapatite composite material that described step (3) silk fiber mineralising obtains, hydroxyapatite becomes nanometer or the bar-shaped silk fiber surface that is attached to of micron to form mineralising.
The present invention utilizes the method to synthesize silk fiber/hydroxyapatite composite material first, is to put into silk fiber before heating synthesizing hydroxylapatite nanometer rods, allows silk fiber and hydroxyapatite nano or micron bar jointly heat.
The present invention adopts with the deposition of silk cellulose fiber for organic formwork regulation and control inorganic ions, widened the source of biomaterial, and silk fiber is easier than silk fibroin solution obtains and preserve.Hydroxyapatite has good biocompatibility, and be the main inorganic composition forming skeleton and tooth, the present invention utilizes Ca (NO
3)
2and Na
3pO
4add silk fiber while generating hydroxyapatite under reaction high temperature, take silk fiber as the formation of template to regulate hydroxyapatite, hydroxyapatite is adhered to and is covered in silk fiber surface.
Present invention achieves the mutual supplement with each other's advantages of silk fiber and hydroxyapatite, at maintenance hydroxyapatite as the mechanical property basis of engineering material of bone tissue improving material, silk fiber/hydroxyapatite composite material is biomaterial of good performance, can be widely used in bone tissue engineer.
Compared with prior art, the present invention has following outstanding feature:
(1) compare the mineralising of silk fibroin solution, silk fiber more easily obtains and preserves, simple to operate, and the source of material is convenient.
(2) synthesizing hydroxylapatite limit in limit completes mineralising, substantially reduces reaction time, and technique is simple, efficient, does not have complicated loaded down with trivial details mineralization process, the time is greatly saved, improves conventional efficient.
(3) only relate to the building-up process of hydroxyapatite in course of reaction, in mineralization process, only produce hydroxyapatite, there is no the pollution of other foreign material.
(4) silk fiber/hydroxyapatite composite material has good biocompatibility, and biological safety is high, can meet the application in biomedicine.
Accompanying drawing explanation
Accompanying drawing 1 is fibroin fiber and hydroxylapatite mineralized about 1500 times of SEM scintigrams in embodiment 1.
Accompanying drawing 2 is fibroin fiber and hydroxylapatite mineralized 50000 times of SEM scintigrams in embodiment 1.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiments of the invention are as follows:
Embodiment 1
In the present embodiment, a kind of mineralization methods of silk fiber in turn includes the following steps.
(1) stripping: take 0.5g raw silk, with the Na of 5%
2cO
3aqueous solution 1L carries out degumming process, degumming process 25 minutes, and this process repeats once again, obtains the fibroin fiber come unstuck;
(2) mineralized liquid is prepared: take 0.5g stearylamine, add 4ml linoleic acid, 16ml ethanol, is stirred to and dissolves completely, adds the Ca (NO of 0.4mol/L
3)
2aqueous solution 7.5ml, stratification, adds the Na of 0.4mol/L
3pO
4aqueous solution 7.5ml, stirs;
(3) mineralization process: the solution fibroin fiber in step (1) being put into step (2), makes solution submergence fibroin fiber, under 100 DEG C of hot conditions, jointly heats 8h;
(4) observe: take out fibroin fiber in step (3), the non-binding constituents on fibroin fiber surface is removed with ethanol purge, then SEM scanning, as shown in Figures 1 and 2, after silk fiber mineralising, hydroxyapatite is incorporated into silk surface, and the length of hydroxyapatite nano rod is about 200nm as seen from the figure.
Embodiment 2
(1) air plasma reason silk fiber, power is process 10min under 100w intensity;
(2) mineralized liquid is prepared: take 0.25g stearylamine, add 2ml linoleic acid, 8ml ethanol, is stirred to and dissolves completely, adds the Ca (NO of 0.4mol/L
3)
2aqueous solution 3.75ml, stratification, adds the Na of 0.4mol/L
3pO
4aqueous solution 3.75ml, stirs;
(3) mineralization process: the solution silk fiber that the plasma treatment in step (1) is crossed being put into step (2), makes solution submergence silk fiber, under 100 DEG C of hot conditions, jointly heats 12h;
(4) observe: take out silk fiber in step (3), remove the non-binding constituents on silk fiber surface with ethanol purge, then SEM scanning.
Embodiment 3
(1) stripping: take 0.2g raw silk, put into the deionized water boiled and come unstuck, degumming process one hour, this process repeats once, obtains the fibroin fiber come unstuck;
(2) mineralized liquid is prepared: take 0.3g stearylamine, add 2ml linoleic acid, 12ml ethanol, is stirred to and dissolves completely, adds the Ca (NO of 0.4mol/L
3)
2aqueous solution 7.5ml, stratification, adds the Na of 0.4mol/L
3pO
4aqueous solution 7.5ml, stirs;
(3) mineralization process: the solution fibroin fiber in step (1) being put into step (2), makes solution submergence fibroin fiber, under 100 DEG C of hot conditions, jointly heats 12h;
(4) observe: take out fibroin fiber in step (3), remove the non-binding constituents on fibroin fiber surface with ethanol purge, then SEM scanning.
Embodiment 4
(1) stripping: take 0.3g raw silk, put into the deionized water boiled and come unstuck, degumming process one hour, this process repeats once, obtains the fibroin fiber come unstuck;
(2) mineralized liquid is prepared: take 0.6g stearylamine, add 8ml linoleic acid, 16ml ethanol, is stirred to and dissolves completely, adds the Ca (NO of 0.4mol/L
3)
2aqueous solution 7.5ml, stratification, adds the Na of 0.4mol/L
3pO
4aqueous solution 7.5ml, stirs;
(3) mineralization process: the solution fibroin fiber in step (1) being put into step (2), makes solution submergence fibroin fiber, under 100 DEG C of hot conditions, jointly heats 6h;
(4) observe: take out fibroin fiber in step (3), remove the non-binding constituents on fibroin fiber surface with ethanol purge, then SEM scanning.
The mineralising time of existing silk fiber is all at 24 ~ 48 hours, and the inventive method is simple to operate, material source is taken conveniently, common heat time heating time can be shortened greatly, by mineralising time shorten to 6 ~ 12 hour, efficiency can be improve, there is no impurity pollution, there is the technical characterstic that good biocompatibility, biological safety etc. are significantly outstanding, the application in biomedicine can be met.
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. a mineralization methods for silk fiber, is characterized in that comprising the steps:
(1) stearylamine is joined in the linoleic acid that volume ratio is 1:2 ~ 6 and alcohol mixed solution, be stirred to and dissolve completely, add Ca (NO
3)
2after aqueous solution stratification, then add Na
3pO
4the aqueous solution, stirs;
(2) added by silk fiber in the solution that step (1) obtains, in silk fiber and step (1), the mass ratio of solution is less than 1:10, makes solution submergence silk fiber, heats 6-12 h under 100 DEG C of hot conditions;
(3) take out silk fiber in step (2), use ethanol purge silk fiber, remove the non-binding constituents on silk fiber surface, realize the mineralising of silk fiber.
2. the mineralization methods of a kind of silk fiber according to claim 1, is characterized in that: described Ca (NO
3)
2ca in the aqueous solution
2+and Na
3pO
4pO in the aqueous solution
4 3-mol ratio 1.67.
3. the mineralization methods of a kind of silk fiber according to claim 1, is characterized in that: the fibroin fiber that in described step (1), silk fiber comprises raw silk, degumming process is crossed or the silk fiber that method of plasma processing obtains.
4. the mineralization methods of a kind of silk fiber according to claim 1, it is characterized in that: in silk fiber/hydroxyapatite composite material that described step (3) silk fiber mineralising obtains, hydroxyapatite become nanometer or micron bar-shaped be attached to silk fiber surface mineralising.
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|---|---|---|---|
| CN201510406788.0A CN104928908B (en) | 2015-07-10 | 2015-07-10 | Method for mineralizing silk fiber |
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| CN201510406788.0A CN104928908B (en) | 2015-07-10 | 2015-07-10 | Method for mineralizing silk fiber |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111266092A (en) * | 2020-01-19 | 2020-06-12 | 浙江大学 | Preparation method of mineralized flat plate silk sewage treatment membrane |
| CN115581801A (en) * | 2022-09-29 | 2023-01-10 | 苏州大学 | Calcium phosphate mineralized silk micro-nano fiber membrane and preparation method thereof |
-
2015
- 2015-07-10 CN CN201510406788.0A patent/CN104928908B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| "纳米羟基磷灰石制备中表面活性剂的应用研究";方伟光，姚成立;《安徽化工》;20141215;第40卷(第6期);第9-13页 * |
| "蚕丝磷酸钙涂层支架的制备和性能";张珂等;《蚌埠医学院学报》;20120615;第37卷(第6期);第727-729页 * |
| 张珂等: ""蚕丝磷酸钙涂层支架的制备和性能"", 《蚌埠医学院学报》 * |
| 方伟光，姚成立: ""纳米羟基磷灰石制备中表面活性剂的应用研究"", 《安徽化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111266092A (en) * | 2020-01-19 | 2020-06-12 | 浙江大学 | Preparation method of mineralized flat plate silk sewage treatment membrane |
| CN115581801A (en) * | 2022-09-29 | 2023-01-10 | 苏州大学 | Calcium phosphate mineralized silk micro-nano fiber membrane and preparation method thereof |
| CN115581801B (en) * | 2022-09-29 | 2024-05-17 | 苏州大学 | Calcium phosphate mineralized silk micro-nano fiber film and preparation method thereof |
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| CN104928908B (en) | 2017-04-12 |
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