CN103013140B - Carbon nano tube/collagen based composite material and preparation method thereof - Google Patents
Carbon nano tube/collagen based composite material and preparation method thereof Download PDFInfo
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- CN103013140B CN103013140B CN201210566573.1A CN201210566573A CN103013140B CN 103013140 B CN103013140 B CN 103013140B CN 201210566573 A CN201210566573 A CN 201210566573A CN 103013140 B CN103013140 B CN 103013140B
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Abstract
The invention discloses a carbon nano tube/collagen based composite material and a preparation method of the composite material. The composite material comprises collagen protein and carbon nano tubes, wherein the content of the collagen protein is 96.0-99.8 percent by mass percentage, and the content of the carbon nano tubes is 0.2-4.0 percent by mass percentage. According to the invention, the obtained carbon nano tube/collagen based composite material is provided with favorable biocompatibility, tissue repair property and extremely low immunogenicity; the required raw materials are easy to get; the conditions of the preparation technology are milder; and the composite material is provided with wide popularization and application value.
Description
Technical field
The invention belongs to nano composite material and preparing technical field thereof, be specifically related to a kind of carbon nanotube/collagen group composite material and preparation method thereof.
Background technology
In recent years along with social population increases severely, the quickening of rhythm of life, lacked (disease) damaged occurred frequently by tumour, infection, physiological function goes down and other cause of disease causes tissue, mankind's unexpected injury that the frequent generation of natural disaster, work accident and the development of automotive industry and the universal of sports cause increases severely and has the trend of rejuvenation.The reparation that the tissue scarce (disease) that these health to the mankind forms great threat above damages all needs guided tissue regeneration's material.
Collagen is the major ingredient of extracellular matrix (ECM), belongs to structural protein, and its appearance makes the research of guided tissue regeneration's material enter a new stage.Collagen has: (1) distinctive reticulated structure, bootable Growth of Cells; (2) no antigen; (3) agglutination can be participated in, and energy Promote cell's growth; (4) physical and mechanical properties is excellent; (5) good biocompatibility; (6) advantage such as degradable, absorption, these advantages be other natural materialss incomparable, therefore collagen is a kind of natural materials of degradable medical guided tissue regeneration of excellent property.
Collagen is in vivo with collagen fibril or the form existence claiming collegen filament, and the fundamental structural unit of collegen filament is tropocollagen molecules, and in carefully bar-shaped, long 300 nm, diameter 1.5 nm, relative molecular weight is 2.85 × 10
5.Each tropocollagen molecule has a peptide chain composition of left hand helix structure by 3, and 3 peptide chains pass through mutual Foldble disk around formation right hand composite screw.Collagen distinctive triple helices structure gives its good biology performance, as the performance of high tensile, biodegradability, low antigenic activity, low irritant and low cell toxicant and Promote cell's growth, also make simultaneously it can with other material, as hydroxyapatite, carbon nanotube and cytokine etc. effectively combine, these characteristics had all become a kind of desirable bio-medical material and pharmaceutical carrier.
In recent years, carbon nanotube (CNTs), owing to having very large specific surface area, can have good cementability with polymer matrix, thus effectively improves the mechanical property of matrix, arouses widespread concern.It is hollow tubule curling based on the plane hexagon graphene that formed by carbon atom, can be divided into multi-walled carbon nano-tubes and Single Walled Carbon Nanotube.Find from microtexture research, the diameter of single-wall carbon nano tube of representative configuration, at 0.5-1.5 nm, is about 100-300 nm, and this is closely similar with the triple-helix structure (diameter 1. 5 nm, long 300 nm) of collegen filament in bone, cartilage.Domestic and international research shows: though CNTs has the advantage of good, the good cell attachment rate of biomechanical property and proliferation rate as single timbering material, but also there is the shortcoming that plasticity-difficulty is comparatively large, can not degrade, therefore, the compound of the material such as CNTs and collagen scaffold is expected to the defect solving itself.In addition, CNTs has very large application potential in nutriment, medicine supply system, can at nutriment, form columnar channel between medicine supply system and cell, the materials such as conveying peptide, protein, plasmid DNA or oligonucleotide, therefore CNTs is likely as carrying the effective carrier of cytokine thus being applied to the Repair of tissue defect such as bone, cartilage.
Present invention incorporates the advantage of natural collagen and CNTs, prepare a kind of carbon nanotube/collagen group composite material with guided tissue regeneration's effect, this material has good biocompatibility, tissue repair performance and extremely low immunogenicity, can be applicable to bone, cartilage etc. and organizes disease defect repair.
Summary of the invention
The object of the present invention is to provide a kind of carbon nanotube/collagen group composite material and preparation method thereof, this matrix material is that a kind of novel tissue with good biocompatibility and tissue repair performance guides twice-laid stuff.
For achieving the above object, the present invention adopts following technical scheme:
A kind of carbon nanotube/collagen group composite material, this matrix material is made up of collagen protein and carbon nanotube, and wherein the mass percentage content of collagen protein is 96.0-99.8%, and the mass percentage content of carbon nanotube is 0.2-4.0%.
Described collagen protein is the collagen protein of collagen of fish skin or pigskin, ox-hide, heel string.
Described carbon nanotube is the Single Walled Carbon Nanotube of modification, or the multi-walled carbon nano-tubes of covalent modified and non-covalent modification.
A kind of method preparing carbon nanotube/collagen group composite material as above comprises the steps:
(1) the raw material machinery being rich in collagen protein is removed subdermal muscle, fat and reticular tissue impurity, clean up after cutting into 1 mm × 1 mm fragment;
(2) with 0.01 mol/L sodium hydroxide and volume fraction be the aqueous isopropanol washing degreasing of the mixing solutions of the hydrogen peroxide of 1%, 10wt%;
(3) be dissolved in the dilute acid soln of pH=2.0-3.0, described acid is acetic acid, propionic acid or propanedioic acid;
(4) add proteolytic enzyme, the mass ratio of collagen protein and proteolytic enzyme is enzymolysis 16-24h at 50-100:1,4-5 DEG C;
(5) in the supernatant liquor of collected by centrifugation, add NaCl or KCl, make final concentration reach 0.9 mo1/L, leave standstill centrifugal 20 min of 10-12 h, 5000 r/min, collect the throw out obtained;
(6) throw out is dissolved in 0.5 mol/L acetic acid solution of 10 times of volumes, collected by centrifugation supernatant liquor;
(7) dialyse 12 h in 0.1 mol/L acetic acid solution of 10 times of volumes, and every 3 h change liquid once, finally extremely neutral with purified water dialysis;
(8) after getting dialysis, collagen and carbon nanotube mix, magnetic agitation 10 h, crosslinked in cross-linking agent solution after lyophilize;
(9) by purified water, the matrix material after crosslinked is fully rinsed, lyophilize again, take out and be placed on 24 h that to pressurize between two pieces of tetrafluoroethylene flat boards and make it smooth, obtain carbon nanotube/collagen group composite material.
Described proteolytic enzyme is stomach en-, trypsinase or papoid.
Described linking agent formula is: 0.2 mol/L ribose+10wt% acetone+2wt% ammoniacal liquor, or formaldehyde, glutaraldehyde, carbonization imines, diepoxides, genipin, one or more in pycnogenols.
In described cross-linking agent solution, the mass percentage of linking agent is 0.3-3%.
Beneficial effect of the present invention is: carbon nanotube/collagen group composite material that the present invention obtains has good biocompatibility, tissue repair performance and extremely low immunogenicity, desired raw material is easy to get, preparation process condition is gentleer, has application value widely.
Accompanying drawing explanation
Fig. 1 is carbon nanotube/collagen group composite material field emission scanning electron microscope figure.
Embodiment
Embodiment 1: prepare carbon nanotube/collagen group composite material, concrete steps are as follows:
(1) the fish-skin machinery being rich in collagen protein being removed the impurity such as subdermal muscle, fat and reticular tissue, cutting into about cleaning up after 1mm x 1 mm fragment;
(2) with 0.01 mol/L sodium hydroxide and containing volume fraction be 1% mixed solution of hydrogen peroxide, 10% aqueous isopropanol washing degreasing;
(3) be dissolved in the acetic acid solution of pH 2.0;
(4) in above-mentioned solution, add proteolytic enzyme, the mass ratio of collagen protein and proteolytic enzyme is 50:1, enzymolysis 24 h at 4 DEG C;
(5) in the supernatant of collected by centrifugation, add NaCl, make final concentration reach 0.9 mo1/L, leave standstill centrifugal 20 min of 12 h, 5000r/min, collect the throw out obtained;
(5) throw out is dissolved in the 0.5mol/L acetic acid solution of 10 times of volumes, collected by centrifugation supernatant;
(7) dialyse 12 h in the 0.1mol/L acetic acid solution of 10 times of volumes, and every 3 h change liquid once, finally extremely neutral with purified water dialysis;
(8) after getting dialysis, collagen mixes by the carbon nanotube of dry weight 96.0% and 4%, magnetic agitation 10 h, crosslinked in cross-linking agent solution after lyophilize, crosslinked fluid formula: 0.2 mol.L
-1ribose+10% acetone+2% ammoniacal liquor;
(8) by purified water, the matrix material after crosslinked is fully rinsed, lyophilize again, take out and be placed on 24 h that to pressurize between two pieces of tetrafluoroethylene flat boards and make it smooth, obtain carbon nanotube/collagen group composite material (see figure 1).
Embodiment 2: prepare carbon nanotube/collagen group composite material, concrete steps are as follows:
(1) the fish-skin machinery being rich in collagen protein being removed the impurity such as subdermal muscle, fat and reticular tissue, cutting into about cleaning up after 1 mm x 1 mm fragment;
(2) with 0.01 mol/L sodium hydroxide and containing volume fraction be 1% mixed solution of hydrogen peroxide, 10% aqueous isopropanol washing degreasing;
(3) be dissolved in the propanedioic acid solution of pH 3.0;
(4) in above-mentioned solution, add proteolytic enzyme, the mass ratio of collagen protein and proteolytic enzyme is 100:1, enzymolysis 16 h at 5 DEG C;
(5) in the supernatant of collected by centrifugation, add KCl, make final concentration reach 0.9 mo1/L, leave standstill centrifugal 20 min of 10 h, 5000r/min, collect the throw out obtained;
(6) throw out is dissolved in the 0.5mol/L acetic acid solution of 10 times of volumes, collected by centrifugation supernatant;
(7) dialyse 12 h in 0.1 mol/L acetic acid solution of 10 times of volumes, and every 3 h change liquid once, finally extremely neutral with purified water dialysis;
(8) after getting dialysis, collagen mixes by the carbon nanotube of dry weight 99.8% and 0.2%, magnetic agitation 10 h, crosslinked in 0.3% formaldehyde solution after lyophilize;
(9) by purified water, the matrix material after crosslinked is fully rinsed, lyophilize again, take out and be placed on 24 h that to pressurize between two pieces of tetrafluoroethylene flat boards and make it smooth, obtain carbon nanotube/collagen group composite material.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. carbon nanotube/collagen group composite material, is characterized in that: this matrix material is made up of collagen protein and carbon nanotube, and wherein the mass percentage content of collagen protein is 96.0-99.8%, and the mass percentage content of carbon nanotube is 0.2-4.0%;
Preparation method comprises the steps:
(1) the raw material machinery being rich in collagen protein is removed subdermal muscle, fat and reticular tissue impurity, clean up after cutting into 1 mm × 1 mm fragment;
(2) with 0.01 mol/L sodium hydroxide and volume fraction be the aqueous isopropanol washing degreasing of the mixing solutions of the hydrogen peroxide of 1%, 10wt%;
(3) be dissolved in the dilute acid soln of pH=2.0-3.0, described acid is acetic acid, propionic acid or propanedioic acid;
(4) add proteolytic enzyme, the mass ratio of collagen protein and proteolytic enzyme is enzymolysis 16-24h at 50-100:1,4-5 DEG C;
(5) in the supernatant liquor of collected by centrifugation, add NaCl or KCl, make final concentration reach 0.9 mo1/L, leave standstill centrifugal 20 min of 10-12 h, 5000 r/min, collect the throw out obtained;
(6) throw out is dissolved in 0.5 mol/L acetic acid solution of 10 times of volumes, collected by centrifugation supernatant liquor;
(7) dialyse 12 h in 0.1 mol/L acetic acid solution of 10 times of volumes, and every 3 h change liquid once, finally extremely neutral with purified water dialysis;
(8) after getting dialysis, collagen and carbon nanotube mix, magnetic agitation 10 h, crosslinked in cross-linking agent solution after lyophilize; Described linking agent formula is: 0.2 mol/L ribose+10wt% acetone+2wt% ammoniacal liquor, or formaldehyde, glutaraldehyde, carbonization imines, diepoxides, genipin, one or more in pycnogenols;
(9) by purified water, the matrix material after crosslinked is fully rinsed, lyophilize again, take out and be placed on 24 h that to pressurize between two pieces of tetrafluoroethylene flat boards and make it smooth, obtain carbon nanotube/collagen group composite material.
2. carbon nanotube/collagen group composite material according to claim 1, is characterized in that: described collagen protein is the collagen protein of collagen of fish skin or pigskin, ox-hide, heel string.
3. carbon nanotube/collagen group composite material according to claim 1, is characterized in that: described carbon nanotube is the Single Walled Carbon Nanotube of modification, or the multi-walled carbon nano-tubes of covalent modified and non-covalent modification.
4. carbon nanotube/collagen group composite material according to claim 1, is characterized in that: described proteolytic enzyme is stomach en-, trypsinase or papoid.
5. carbon nanotube/collagen group composite material according to claim 1, is characterized in that: in described cross-linking agent solution, the mass percentage of linking agent is 0.3-3%.
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| CN106189027B (en) * | 2016-06-03 | 2017-10-24 | 深圳市前海金卓生物技术有限公司 | A kind of biological brake |
| CN106860916B (en) * | 2017-04-06 | 2020-06-12 | 福州大学 | GO/nHA/collagen composite bone repair material and preparation method thereof |
| CN111135344A (en) * | 2020-02-27 | 2020-05-12 | 福州大学 | Scaffold for repairing carbon nano tube/collagen-based cartilage of composite albumin and preparation method thereof |
| CN112812689B (en) * | 2021-01-28 | 2021-12-07 | 浙江大学 | Iontophoresis electrode based on collagen/nano-carbon composite drug-loaded conductive coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210019A (en) * | 1998-09-10 | 1999-03-10 | 战丽芬 | Medical collagen sponge and manufacture thereof |
| CN101092449A (en) * | 2007-06-18 | 2007-12-26 | 南京农业大学 | Technique for preparing collagen of freshwater fish skin |
| CN101648989A (en) * | 2008-08-15 | 2010-02-17 | 双美生物科技股份有限公司 | Long-acting type collagen and method for preparing same |
| CN101693125A (en) * | 2009-10-12 | 2010-04-14 | 北京科技大学 | Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel |
| CN102190894A (en) * | 2011-03-25 | 2011-09-21 | 郑州大学 | Method for preparing collagen-based composite material |
| CN102363798A (en) * | 2011-11-15 | 2012-02-29 | 无锡贝迪生物工程有限公司 | Preparation process for collagen sponge |
| CN102416195A (en) * | 2010-09-28 | 2012-04-18 | 北京益而康生物工程开发中心 | Preparation method of collagen sponge |
-
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- 2012-12-25 CN CN201210566573.1A patent/CN103013140B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210019A (en) * | 1998-09-10 | 1999-03-10 | 战丽芬 | Medical collagen sponge and manufacture thereof |
| CN101092449A (en) * | 2007-06-18 | 2007-12-26 | 南京农业大学 | Technique for preparing collagen of freshwater fish skin |
| CN101648989A (en) * | 2008-08-15 | 2010-02-17 | 双美生物科技股份有限公司 | Long-acting type collagen and method for preparing same |
| CN101693125A (en) * | 2009-10-12 | 2010-04-14 | 北京科技大学 | Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel |
| CN102416195A (en) * | 2010-09-28 | 2012-04-18 | 北京益而康生物工程开发中心 | Preparation method of collagen sponge |
| CN102190894A (en) * | 2011-03-25 | 2011-09-21 | 郑州大学 | Method for preparing collagen-based composite material |
| CN102363798A (en) * | 2011-11-15 | 2012-02-29 | 无锡贝迪生物工程有限公司 | Preparation process for collagen sponge |
Non-Patent Citations (1)
| Title |
|---|
| Collagen–carbon nanotube composite materials as scaffolds in tissue engineering;Rebecca A. MacDonald et al.;《Journal of Biomedical Materials Research Part A》;20050901;第74A卷(第3期);490-491 * |
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