CN106668946A - Carbon nano-tube/chitosan/collagen composite scaffold material and preparation thereof - Google Patents

Carbon nano-tube/chitosan/collagen composite scaffold material and preparation thereof Download PDF

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Publication number
CN106668946A
CN106668946A CN201611126200.7A CN201611126200A CN106668946A CN 106668946 A CN106668946 A CN 106668946A CN 201611126200 A CN201611126200 A CN 201611126200A CN 106668946 A CN106668946 A CN 106668946A
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China
Prior art keywords
chitosan
collagen
support frame
carbon nano
frame material
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Pending
Application number
CN201611126200.7A
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Chinese (zh)
Inventor
吴翔
汪云
钱忠
陆尔松
孟金华
徐文海
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Tianchang Tianlong Pump Valve Complete Equipment Factory
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Tianchang Tianlong Pump Valve Complete Equipment Factory
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Priority to CN201611126200.7A priority Critical patent/CN106668946A/en
Publication of CN106668946A publication Critical patent/CN106668946A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/443Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon fillers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602Type of release, e.g. controlled, sustained, slow

Abstract

The invention belongs to the field of tissue engineering materials, and in particular relates to a carbon nano-tube/chitosan/collagen composite scaffold material and preparation thereof. The preparation comprises the following steps: mixing high-concentration chitosan, a collagen solution and a carbon nano-tube, and performing the cross-linked self-assembly, wherein the obtained compound gathers respective advantages of the carbon nano-tube, the chitosan and the collagen after freeze-drying, and has excellent low antigenicity, low irritation and low cytotoxicity, and is capable of promoting cell growth and mechanical property; the carbon nano-tube/chitosan/collagen composite scaffold material is of a three-dimensional porous structure, is provided with multiple pores, has large specific surface area, and is capable of further carrying the medicine or cell growth factors, thereby achieving a slow-release effect.

Description

A kind of Carbon Nanotubes/Chitosan/collagen compound support frame material and its preparation
Technical field
The invention belongs to tissue engineering material field, more particularly to a kind of Carbon Nanotubes/Chitosan/collagen composite support Frame material and its preparation.
Background technology
Shitosan, also known as chitosan, is that the chitin being widely present by nature is obtained by deacetylation , chemical name is Chitosan (1-4) -2- amino-B-D glucose, and shitosan possesses excellent biological functionality and phase Capacitive, blood compatibility, security, microbic resolvability etc., are widely used in biological medicine, food, chemical industry, cosmetics, water The numerous areas such as treatment, METAL EXTRACTION and recovery.Under given conditions, shitosan can hydrolyze, be alkylated, being acylated, The chemical reactions such as carboxy methylation, sulfonation, nitrification, halogenation, oxidation, reduction, condensation and complexing, can generate various with different performance Chitosan derivatives, so as to expand the range of application of shitosan.
CNT is lightweight as monodimension nanometer material, and hexagonal structure connection is perfect, with many abnormal power , electricity and chemical property.And used as one kind of carbon material, CNT also possesses excellent biocompatibility.In general, SWCN has chemical inertness higher, and its surface wants purer, and multi-wall carbon nano-tube pipe surface will vivaciously much, It is combined with substantial amounts of surface group, such as carboxyl.CNT has a good mechanical property, and tensile strength reaches 50~ 200GPa, is 100 times of steel, and density but only has the 1/6 of steel, an order of magnitude at least higher than ordinary graphite fiber;Its elasticity Modulus is up to 1TPa, and the elastic modelling quantity with diamond is suitable, about 5 times of steel.
Collagen is boiomacromolecule, the main component in animal connective tissue, be also mammal in-vivo content most The many, functional protein that distribution is most wide, collagen is because living with good biocompatibility, biodegradable and biology Property, therefore be widely applied in fields such as food, medicine, organizational project, cosmetics.
It is the three-dimensional porous knot of cell growth conveying nutrition and excretion metabolism product in organizational project that biological support refers to The cell carrier of structure.Therefore timbering material usually requires that possess good biocompatibility, three-dimensional porous structure and certain power Learn performance.
Biologic bracket material of the prior art is divided into natural material and synthetic material, and natural material often has excellent Good biocompatibility, but mechanical property has often been short of, and synthetic material biocompatibility is not good enough, or do not possess Adaptable mechanical property.
The content of the invention
The present invention is to solve that biologic bracket material biocompatibility in the prior art is bad, the not good technology of mechanical property A kind of problem, there is provided compound support frame material for having superior bio compatibility, three-dimensional porous structure and mechanical property concurrently.
To solve the above problems, technical scheme is as follows:
A kind of Carbon Nanotubes/Chitosan/collagen compound support frame material, is made up of the raw material of following weight portion:
Shitosan:35-48 parts;
Collagen:35-48 parts;
CNT:4-30 parts.
Preferably, the CNT is multi-walled carbon nano-tubes, and a diameter of 20-40 nm, length is 2-5 microns.
Shitosan have biology can battle array solution, Bc, biological non-toxicity the features such as, but mechanical property is low;Collagen Albumen possesses excellent biodegradability, biocompatibility, low antigenicity, low irritant and low cytotoxicity, and promotes The performances such as cell growth, but there is also the low problem of mechanical strength;Multi-walled carbon nano-tubes possesses excellent mechanical property and biology Compatibility;The shitosan of high concentration, collagen solution and a small amount of CNT be compound, and its is excellent for obtained composite set Point, with excellent low antigenicity, low irritant and low cytotoxicity, and promotes cell growth and mechanical property.
Preferably, the Carbon Nanotubes/Chitosan/collagen compound support frame material, by the raw material group of following weight portion Into:
Shitosan:42 parts;
Collagen:42 parts;
CNT:8 parts.
A kind of preparation method of Carbon Nanotubes/Chitosan/collagen compound support frame material, comprises the following steps:
A. in dissolving the chitosan in the acetum that concentration is 1%;
B. by multi-walled carbon nano-tubes add 15 mg/mL cetyl trimethylammonium bromide solutions in, be well mixed after, ultrasound 4 Hour, multi-walled carbon nano-tubes concentration is 1-4 mg/mL;
C. step A, B is obtained dissolving mixing, ultrasound 3 hours;
D. collagen is dissolved in the mixed solution of step C, is stirred 24 hours under the conditions of 35 DEG C of water-bath;
E. by mixed solution freeze-drying obtained in step D, Carbon Nanotubes/Chitosan/collagen compound support frame material is obtained.
The CNT of the shitosan, collagen solution and cetyl trimethylammonium bromide modification of high concentration possesses good Good adhesion, can crosslink and self assembly after mixing.
Preferably, appropriate crosslinking agent is added in mixed solution described in step D so that shitosan, collagen solution and carbon Nanotube is preferably crosslinked, and forms the more stable compound of structure.
Preferably, the crosslinking agent, it is characterised in that glutaraldehyde, Carbodiimides or alkylene oxide base class crosslinking agent, hands over The mass concentration for joining solution is 0.1%-1%.
Preferably, the lyophilisation condition of the step E is:Under vacuum condition, temperature is -140 DEG C -- 100 DEG C, drying time 6-12 hours.After lyophilized, products therefrom is three-dimensional porous structure, and hole is more, and specific surface area is big, can further carry medicine or Porcine HGF, reaches the effect of sustained release.
Relative to prior art, advantages of the present invention is as follows, a kind of Carbon Nanotubes/Chitosan/collagen of the invention Compound support frame material set CNT, shitosan and the respective advantage of collagen, with excellent low antigenicity, low stimulation Property and low cytotoxicity, and promote cell growth and mechanical property, the shitosan of high concentration, collagen solution and carbon nanometer For good adhesion, the lyophilized product for obtaining is three-dimensional porous structure to pipe, and hole is more, and specific surface area is big, can further take Medicine or Porcine HGF are carried, the effect of sustained release is reached.
Specific embodiment
Embodiment 1:
A kind of Carbon Nanotubes/Chitosan/collagen compound support frame material, is made up of the raw material of following weight portion:
Shitosan:35-48 parts;
Collagen:35-48 parts;
CNT:4-30 parts.
Preferably, the CNT is multi-walled carbon nano-tubes, and a diameter of 20-40 nm, length is 2-5 microns.
Shitosan have biology can battle array solution, Bc, biological non-toxicity the features such as, but mechanical property is low;Collagen Albumen possesses excellent biodegradability, biocompatibility, low antigenicity, low irritant and low cytotoxicity, and promotes The performances such as cell growth, but there is also the low problem of mechanical strength;Multi-walled carbon nano-tubes possesses excellent mechanical property and biology Compatibility;The shitosan of high concentration, collagen solution and a small amount of CNT be compound, and its is excellent for obtained composite set Point, with excellent low antigenicity, low irritant and low cytotoxicity, and promotes cell growth and mechanical property.
Embodiment 2:
A kind of Carbon Nanotubes/Chitosan/collagen compound support frame material, is made up of the raw material of following weight portion:
Shitosan:42 parts;
Collagen:42 parts;
CNT:8 parts.
Embodiment 3:
A kind of preparation method of Carbon Nanotubes/Chitosan/collagen compound support frame material, comprises the following steps:
A. in dissolving the chitosan in the acetum that concentration is 1%;
B. by multi-walled carbon nano-tubes add 15 mg/mL cetyl trimethylammonium bromide solutions in, be well mixed after, ultrasound 4 Hour, multi-walled carbon nano-tubes concentration is 1-4 mg/mL;
C. step A, B is obtained dissolving mixing, ultrasound 3 hours;
D. collagen is dissolved in the mixed solution of step C, is stirred 24 hours under the conditions of 35 DEG C of water-bath;
E. by mixed solution freeze-drying obtained in step D, Carbon Nanotubes/Chitosan/collagen compound support frame material is obtained.
The CNT of the shitosan, collagen solution and cetyl trimethylammonium bromide modification of high concentration possesses good Good adhesion, can crosslink and self assembly after mixing.
Preferably, appropriate crosslinking agent is added in mixed solution described in step D so that shitosan, collagen solution and carbon Nanotube is preferably crosslinked, and forms the more stable compound of structure.
Preferably, the crosslinking agent, it is characterised in that glutaraldehyde, Carbodiimides or alkylene oxide base class crosslinking agent, hands over The mass concentration for joining solution is 0.1%-1%.
Preferably, the lyophilisation condition of the step E is:Under vacuum condition, temperature is -140 DEG C -- 100 DEG C, drying time 6-12 hours.After lyophilized, products therefrom is three-dimensional porous structure, and hole is more, and specific surface area is big, can further carry medicine or Porcine HGF, reaches the effect of sustained release.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, it is not of the invention for limiting Protection domain, the equivalent made on the basis of the above or replacement belong to protection scope of the present invention.

Claims (6)

1. a kind of Carbon Nanotubes/Chitosan/collagen compound support frame material, it is characterised in that by the raw material of following weight portion Composition:
Shitosan:35-48 parts;
Collagen:35-48 parts;
CNT:4-30 parts.
2. Carbon Nanotubes/Chitosan as claimed in claim 1/collagen compound support frame material, it is characterised in that the carbon Nanotube is multi-walled carbon nano-tubes, a diameter of 20-40 nm, and length is 2-5 microns.
3. the preparation method of a kind of Carbon Nanotubes/Chitosan/collagen compound support frame material, it is characterised in that including following Step:
A. in dissolving the chitosan in the acetum that concentration is 1%;
B. by multi-walled carbon nano-tubes add 15 mg/mL cetyl trimethylammonium bromide solutions in, be well mixed after, ultrasound 4 Hour, multi-walled carbon nano-tubes concentration is 2-15 mg/mL;
C. step A, B is obtained dissolving mixing, ultrasound 3 hours;
D. collagen is dissolved in the mixed solution of step C, is stirred 24 hours under the conditions of 35 DEG C of water-bath;
E. by mixed solution freeze-drying obtained in step D, Carbon Nanotubes/Chitosan/collagen compound support frame material is obtained.
4. the preparation method of Carbon Nanotubes/Chitosan as claimed in claim 3/collagen compound support frame material, its feature It is to add crosslinking agent in mixed solution described in step D.
5. the preparation method of Carbon Nanotubes/Chitosan as claimed in claim 4/collagen compound support frame material, its feature It is, the crosslinking agent, it is characterised in that glutaraldehyde, Carbodiimides or alkylene oxide base class crosslinking agent, the matter of crosslinker solution Amount concentration is 0.1%-1%.
6. the preparation method of Carbon Nanotubes/Chitosan as claimed in claim 5/collagen compound support frame material, its feature It is that the lyophilisation condition of the step E is:Under vacuum condition, temperature is -140 DEG C -- 100 DEG C, drying time 6-12 hours.
CN201611126200.7A 2016-12-09 2016-12-09 Carbon nano-tube/chitosan/collagen composite scaffold material and preparation thereof Pending CN106668946A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107537063A (en) * 2017-07-17 2018-01-05 大连理工大学 A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof
CN107737376A (en) * 2017-10-31 2018-02-27 无锡中科光远生物材料有限公司 A kind of preparation method of conductive collagen cardiac patch
CN110801513A (en) * 2019-12-17 2020-02-18 河南汇博医疗股份有限公司 Composite sustained-release particle loaded with growth factor and preparation method thereof
CN115124987A (en) * 2022-06-13 2022-09-30 陕西延长石油(集团)有限责任公司 Long-acting hypersalinity-resistant low-temperature-resistant solid foam scrubbing agent for natural gas ground gathering and transportation pipeline and preparation method thereof
CN115715824A (en) * 2022-10-12 2023-02-28 杭州洛兮生物科技有限公司 Bone scaffold material based on modified single-walled carbon nanotubes and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103196965A (en) * 2013-03-18 2013-07-10 北京科技大学 Method for preparing carbon nanotube composite conductive hydrogel coating modified electrode
CN104147643A (en) * 2014-08-06 2014-11-19 江苏双林海洋生物药业有限公司 Method for preparing conductive tissue engineering scaffold of chitosan and carbon nanometer tube

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103196965A (en) * 2013-03-18 2013-07-10 北京科技大学 Method for preparing carbon nanotube composite conductive hydrogel coating modified electrode
CN104147643A (en) * 2014-08-06 2014-11-19 江苏双林海洋生物药业有限公司 Method for preparing conductive tissue engineering scaffold of chitosan and carbon nanometer tube

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107537063A (en) * 2017-07-17 2018-01-05 大连理工大学 A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof
CN107537063B (en) * 2017-07-17 2019-10-11 大连理工大学 A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof
CN107737376A (en) * 2017-10-31 2018-02-27 无锡中科光远生物材料有限公司 A kind of preparation method of conductive collagen cardiac patch
CN110801513A (en) * 2019-12-17 2020-02-18 河南汇博医疗股份有限公司 Composite sustained-release particle loaded with growth factor and preparation method thereof
CN115124987A (en) * 2022-06-13 2022-09-30 陕西延长石油(集团)有限责任公司 Long-acting hypersalinity-resistant low-temperature-resistant solid foam scrubbing agent for natural gas ground gathering and transportation pipeline and preparation method thereof
CN115715824A (en) * 2022-10-12 2023-02-28 杭州洛兮生物科技有限公司 Bone scaffold material based on modified single-walled carbon nanotubes and preparation method thereof

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