CN105536075A - Nano-micron fiber, chitosan and polylactic acid composite stent and making method thereof - Google Patents

Nano-micron fiber, chitosan and polylactic acid composite stent and making method thereof Download PDF

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CN105536075A
CN105536075A CN201610106720.5A CN201610106720A CN105536075A CN 105536075 A CN105536075 A CN 105536075A CN 201610106720 A CN201610106720 A CN 201610106720A CN 105536075 A CN105536075 A CN 105536075A
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chitosan
polylactic acid
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micron
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楼涛
汪学军
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Qingdao University
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    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
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    • 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
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
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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
    • A61L27/50Materials 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
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    • 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
    • A61L31/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
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    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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    • AHUMAN NECESSITIES
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    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16Biologically active materials, e.g. therapeutic substances
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    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract

The invention relates to a nano-micron fiber, chitosan and polylactic acid composite stent and a making method thereof. According to the making method, a nanometer chitosan and polylactic acid composite fiber membrane and a micrometer chitosan and polylactic acid composite fiber membrane are subjected to electrostatic spinning under certain conditions; after the composite fiber membranes are subjected to alkali washing and air drying, the nanometer fiber membrane and the micrometer fiber membrane are cut into short fibers in water at a high speed according to a certain proportion; after sample separation, freezing forming is performed at the temperature of -18 DEG C, and then freezing drying is performed to obtain the nano-micron fiber, chitosan and polylactic acid composite three-dimensional stent. Defects of chitosan and polylactic acid are overcome after chitosan and polylactic acid are compounded. Through the making method, the process is simple, the stent has a micro-nano scale in fiber diameter, and the composite stent has good biological properties and mechanical properties.

Description

A kind of nano micron fibre chitosan polylactic acid compound rest and preparation method thereof
Technical field
The present invention relates to a kind of nano micron fibre chitosan polylactic acid compound rest and preparation method thereof, belong to biology medical material technical field.
Background technology
Chitosan is as a kind of cation alkaline polysaccharide, the polysaccharose substance such as chondroitin sulfate and hyaluronic acid of similar in human body, can be degraded and absorbed in vivo, and have pain relieving, hemostasis, antibacterial, promote wound healing, reduce the excellent specific property such as cicatrix have important application in biomedical materials field at present.The people such as SundararajanV adopt phase detachment technique to prepare chitosan stent first, and its structure is tens of lamellar honeycomb textures to hundreds of micron thickness, has good biology performance (Biomaterials, 1999; 20:1133-1142), but chitosan is be easy to swelling as the major defect of timbering material.A kind of synthetic polymer timbering material that polylactic acid is ratified the earliest as U.S. FDA; have nontoxic, good with human compatibility, the advantage such as degradablely can to absorb in vivo; be widely used in the reparation (LeeEJ etc. of the tissues such as bone, cartilage, blood vessel and skin and organ; AnnBiomedEng, 2014; 42 (2): 323), polylactic acid hydrophobicity is strong, and cellular affinity is poor, and therefore chitosan and polylactic acid compound can overcome both shortcomings.It is composite porous and preparation method thereof that Li Geng discloses a kind of chitosan-polylactic acid, shows that the composite of chitosan and polylactic acid has good performance (CN102757625A).
Research shows that nano fiber scaffold has larger specific surface area, can provide the better condition of cell adhesion and differentiation, but simple nanofiber mechanical strength is lower, cannot bear the mechanical loading of stent implantation procedure.Comparatively speaking, micrometer fibers support has good mechanical property.Therefore, three-dimensional rack fibre diameter with micro nanometer fiber has good biocompatibility and mechanical property.The method that the many employings of current researcher are separated prepares three-dimensional rack, but its fibre diameter uncontrollable, or adopt the method for electrostatic spinning to obtain the fiber membrane of two dimension, but the 3 D chitosan polylactic acid compound rest preparation method how preparing micro nanometer fiber there is not yet report.
Summary of the invention
Main imagination of the present invention adopts the method for electrostatic spinning to prepare nanometer and micron chitosan PLA Composite Fiber thin film respectively, according to a certain ratio by nanometer and the mixing of micron composite cellulosic membrane, and laminated film high speed shear is become short fiber, after dividing sample, freeze forming, obtains nano micron fibre chitosan polylactic acid complex three-dimensional support through lyophilization.
In the present invention the preparation method of nano micron fibre chitosan polylactic acid complex three-dimensional support specific as follows described in.
(1) electrostatic spinning nano chitin fiber film: preparation chitosan 5.0% solution, solvent be trifluoroacetic acid with the mixture of diox, volume ratio is 70:30; Preparation polylactic acid 10.0% solution, solvent be chloroform with the mixture of diox, volume ratio is 70:30.Chitosan and PLA solution are added respectively in two syringes, connected by two syringes with two-in-one syringe needle, the voltage passing to 20 ~ 25kV carries out spinning.
(2) electrostatic spinning micron chitin fiber film: preparation chitosan 7.5% solution, solvent be trifluoroacetic acid with the mixture of diox, volume ratio is 90:10; Preparation polylactic acid 20.0% solution, solvent be chloroform with the mixture of diox, volume ratio is 90:10.Chitosan and PLA solution are added respectively in two syringes, connected by two syringes with two-in-one syringe needle, the voltage passing to 12 ~ 15kV carries out spinning.
(3) nanometer obtained by electrostatic spinning and micron chitosan PLA Composite Fiber film are immersed in the solvent removed in the sodium hydroxide solution of 0.5mol/L and do not volatilize, and wash air-dry rear stand-by.
(4) take quantitative nanometer and micron chitosan PLA Composite Fiber film respectively, join in quantitative water, cut into short fiber in water high speed.
(5) divide sample in weighing botle, freeze forming at-18 DEG C.
(6) nano micron fibre chitosan polylactic acid compound rest can be obtained after lyophilization.
The nano micron fibre chitosan polylactic acid compound rest outward appearance that the present invention obtains is white disk, and its shape and height can adopt different containers and point sample volume-adjustment in point sample.The compound of chitosan and polylactic acid can overcome both shortcomings, and support has better combination property.Obtain mainly through electrostatic spinning in preparation method and receive the fiber of micro-meter scale, also can adjust spinning condition in preparation easily and obtain nanometer and micron chitosan PLA Composite Fiber.This support has micro-nano-scale on fibre diameter, gives the good biocompatibility of support and mechanical strength.This preparation method technique is simple, and be easy to the chitosan PLA Composite Fiber obtaining different-diameter, compared to simple method of electrostatic spinning, this method also easily can prepare the support of three dimensional structure.
Detailed description of the invention
Below in conjunction with specific embodiment, content of the present invention is further described, but implementation of the present invention is not limited thereto.
Embodiment 1: trifluoroacetic acid and the 3ml diox of getting 7ml respectively, mix homogeneously, takes 0.5g chitosan, stirring and dissolving, leaves standstill 12 hours.Get chloroform and the 3ml diox of 7ml respectively, mix homogeneously, takes 1.0g polylactic acid, stirring and dissolving, leaves standstill 12 hours.Chitosan and PLA solution are joined respectively in two syringes, with two-in-one syringe needle, two syringes are connected, pass to the voltage spinning of 20kV, be collected on the aluminium foil of ground connection, can obtain chitosan polylactic acid nano composite fiber thin film, fibre diameter is between 50-500nm.Get trifluoroacetic acid and the 1ml diox of 9ml respectively, mix homogeneously, takes 0.75g chitosan, stirring and dissolving, leaves standstill 12 hours.Get chloroform and the 1ml diox of 9ml respectively, mix homogeneously, takes 2.0g polylactic acid, stirring and dissolving, leaves standstill 12 hours.Chitosan and PLA solution are joined respectively in two syringes, with two-in-one syringe needle, two syringes are connected, pass to the voltage spinning of 15kV, be collected on the aluminium foil of ground connection, can obtain chitosan polylactic acid micron composite fiber thin film, fibre diameter is between 1-10 μm.The nanometer obtained by electrostatic spinning and micrometer fibers film are immersed in the solvent removed in the sodium hydroxide solution of 0.5mol/L and do not volatilize, and wash air-dry.Take 0.2g and 0.8g nanometer and micron chitosan PLA Composite Fiber film respectively, short fiber is cut in 100ml water high speed, divide sample in weighing botle, freeze forming at-18 DEG C, can obtain nano micron fibre chitosan polylactic acid complex three-dimensional support in freeze dryer after lyophilizing.
Embodiment 2: trifluoroacetic acid and the 6ml diox of getting 14ml respectively, mix homogeneously, takes 1.0g chitosan, stirring and dissolving, leaves standstill 12 hours.Get chloroform and the 6ml diox of 14ml respectively, mix homogeneously, takes 2.0g polylactic acid, stirring and dissolving, leaves standstill 12 hours.Chitosan and PLA solution are joined respectively in two syringes, with two-in-one syringe needle, two syringes are connected, pass to the voltage spinning of 25kV, be collected on the aluminium foil of ground connection, can obtain chitosan polylactic acid nano composite fiber thin film, fibre diameter is between 50-500nm.Get trifluoroacetic acid and the 1ml diox of 9ml respectively, mix homogeneously, takes 0.75g chitosan, stirring and dissolving, leaves standstill 12 hours.Get chloroform and the 1ml diox of 9ml respectively, mix homogeneously, takes 2.0g polylactic acid, stirring and dissolving, leaves standstill 12 hours.Chitosan and PLA solution are joined respectively in two syringes, with two-in-one syringe needle, two syringes are connected, pass to the voltage spinning of 12kV, be collected on the aluminium foil of ground connection, can obtain chitosan polylactic acid micron composite fiber thin film, fibre diameter is between 1-10 μm.The nanometer obtained by electrostatic spinning and micrometer fibers film are immersed in the solvent removed in the sodium hydroxide solution of 0.5mol/L and do not volatilize, and wash air-dry.Take 2.4g and 0.6g nanometer and micron chitosan PLA Composite Fiber film respectively, short fiber is cut in 100ml water high speed, divide sample in weighing botle, freeze forming at-18 DEG C, can obtain nano micron fibre chitosan polylactic acid complex three-dimensional support in freeze dryer after lyophilizing.

Claims (5)

1. nano micron fibre chitosan polylactic acid compound rest and preparation method thereof, it is characterized in that distinguishing electrostatic spinning nano and micron chitosan PLA Composite Fiber film under certain condition, in the sodium hydroxide solution of 0.5mol/L, remove the solvent do not volatilized and wash air-dry after, according to a certain ratio nanometer and micron chitosan PLA Composite Fiber film are cut into short fiber in water high speed, after dividing sample, freeze forming, obtains nano micron fibre chitosan polylactic acid complex three-dimensional support through lyophilization.
2. nano micron fibre chitosan polylactic acid compound rest according to claim 1 and preparation method thereof, it is characterized in that used chitosan molecule amount is between 20 ~ 400,000, polylactic acid molecule amount is between 5 ~ 100,000.
3. nano micron fibre chitosan polylactic acid compound rest according to claim 1 and preparation method thereof, when it is characterized in that Electrospun nano-fibers film, chitosan concentration is 5.0%, solvent is that trifluoroacetic acid is with the mixture of diox, volume ratio is 70:30, and PLA concentration is 10.0%, and solvent is that chloroform is with the mixture of diox, volume ratio is 70:30, and spinning voltage is 20 ~ 25kV.
4. nano micron fibre chitosan polylactic acid compound rest according to claim 1 and preparation method thereof, when it is characterized in that electrostatic spinning micron chitin fiber film, chitosan concentration is 7.5%, solvent is that trifluoroacetic acid is with the mixture of diox, volume ratio is 90:10, and PLA concentration is 20.0%, and solvent is that chloroform is with the mixture of diox, volume ratio is 90:10, and spinning voltage is 12 ~ 15kV.
5. nano micron fibre chitosan polylactic acid compound rest according to claim 1 and preparation method thereof, it is characterized in that the mass ratio of Nano chitosan PLA Composite Fiber and micron chitosan PLA Composite Fiber is between 20:80 to 80:20, the total concentration of chitosan polylactic acid nano micrometer fibers in water is between 1 ~ 3%.
CN201610106720.5A 2016-02-27 2016-02-27 A kind of nano micron fibre chitosan polylactic acid compound rest and preparation method thereof Expired - Fee Related CN105536075B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107475797A (en) * 2016-06-08 2017-12-15 南京理工大学 A kind of magnetic Nano chopped fiber and preparation method thereof
WO2018227587A1 (en) * 2017-06-16 2018-12-20 深圳大学 Method for preparing anti-smog nonwoven fabric
CN109381747A (en) * 2017-08-10 2019-02-26 沙冰娟 A kind of preparation method of polylactic acid-chitose fiber scaffold material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285424A (en) * 2013-05-27 2013-09-11 东华大学 Three-dimensional fiber-based aerogel tissue engineering scaffold and preparation method thereof
CN103691005A (en) * 2013-12-24 2014-04-02 华东交通大学 Micro-nanofiber tissue engineering scaffold and preparation method thereof
WO2014160019A1 (en) * 2013-03-14 2014-10-02 Lifenet Health Aligned fiber and method of use thereof
CN104888278A (en) * 2015-05-20 2015-09-09 东华大学 Nanometer/micrometer fiber three-dimensional porous structure support material and preparation and application of support material
CN105107022A (en) * 2015-09-21 2015-12-02 东华大学 Preparation method for nanofiber porous scaffold having compression elasticity in wet state

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014160019A1 (en) * 2013-03-14 2014-10-02 Lifenet Health Aligned fiber and method of use thereof
CN103285424A (en) * 2013-05-27 2013-09-11 东华大学 Three-dimensional fiber-based aerogel tissue engineering scaffold and preparation method thereof
CN103691005A (en) * 2013-12-24 2014-04-02 华东交通大学 Micro-nanofiber tissue engineering scaffold and preparation method thereof
CN104888278A (en) * 2015-05-20 2015-09-09 东华大学 Nanometer/micrometer fiber three-dimensional porous structure support material and preparation and application of support material
CN105107022A (en) * 2015-09-21 2015-12-02 东华大学 Preparation method for nanofiber porous scaffold having compression elasticity in wet state

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107475797A (en) * 2016-06-08 2017-12-15 南京理工大学 A kind of magnetic Nano chopped fiber and preparation method thereof
WO2018227587A1 (en) * 2017-06-16 2018-12-20 深圳大学 Method for preparing anti-smog nonwoven fabric
CN109381747A (en) * 2017-08-10 2019-02-26 沙冰娟 A kind of preparation method of polylactic acid-chitose fiber scaffold material

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