CN107158475A - One kind stress activated fibre film and preparation method thereof - Google Patents

One kind stress activated fibre film and preparation method thereof Download PDF

Info

Publication number
CN107158475A
CN107158475A CN201710409812.5A CN201710409812A CN107158475A CN 107158475 A CN107158475 A CN 107158475A CN 201710409812 A CN201710409812 A CN 201710409812A CN 107158475 A CN107158475 A CN 107158475A
Authority
CN
China
Prior art keywords
high polymer
synthetic material
fibroin albumen
medical high
spinning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710409812.5A
Other languages
Chinese (zh)
Inventor
柏自奎
周应山
向春
彭国富
龚年华
郭强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
People's Good Fortune Pharmaceutical Group Medical Supplies Co Ltd
Original Assignee
People's Good Fortune Pharmaceutical Group Medical Supplies Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by People's Good Fortune Pharmaceutical Group Medical Supplies Co Ltd filed Critical People's Good Fortune Pharmaceutical Group Medical Supplies Co Ltd
Priority to CN201710409812.5A priority Critical patent/CN107158475A/en
Publication of CN107158475A publication Critical patent/CN107158475A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • A61L27/14Macromolecular materials
    • A61L27/16Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/14Macromolecular materials
    • A61L27/22Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/227Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
    • 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
    • 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
    • A61L31/043Proteins; Polypeptides; Degradation products thereof
    • A61L31/047Other specific proteins or polypeptides not covered by A61L31/044 - A61L31/046
    • 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
    • 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
    • A61L31/048Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • A61L31/146Porous materials, e.g. foams or sponges

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

The present invention relates to a kind of composite nano fiber by polyvinylidene fluoride nanometer fiber and fibroin albumen and medical high polymer synthetic material constitute stress activated fibre film and preparation method thereof, belong to biomedical materials field, described stress the mass ratio of fibroin albumen and medical high polymer synthetic material be 1/20~1/1 in activated fibre film, the mass ratio of Kynoar and medical high polymer synthetic material is 1/99~5/95, using Static Spinning silk fibroin protein solution or fibroin albumen powder dispersion and the mixed solution and Kynoar solution of medical high polymer synthetic material solution composition, obtain the IPN non-woven constructions tunica fibrosa of the composite nano fiber and polyvinylidene fluoride nanometer fiber composition of fibroin albumen and medical high polymer synthetic material, the tunica fibrosa has uniform and stable micro-structural, good biocompatibility, it can be widely applied to tissue engineering bracket and wound or scar repair material, what wherein the good piezoelectricity of polyvinylidene fluoride nanometer fiber assigned tunica fibrosa stress activity.

Description

One kind stress activated fibre film and preparation method thereof
Technical field
The present invention relates to one kind stress activated fibre film and preparation method thereof, belong to biomedical materials field.
Background technology
Stress activity generally refer to organism and stimulate to external world react, and change or transmit the characteristic of this stimulation It is referred to as.Tunica fibrosa is widely used the tissue engineering bracket and surface wound repaired in in-vivo tissue or scar nursing.But mesh The preceding tissue engineering bracket for in-vivo tissue reparation, which is appointed, to be confined to based on the reparation of occupancy replacement or occupancy reconstruction, for tissue Growth provide physical space and matrix environment, can not as biological tissue with physiological stress, electromagnetic action, physics drawing-off, Compression or biochemical stimulate and make accordingly stress activity, the tunica fibrosa nursed for surface wound or scar is also limited to the surface of a wound and inhales Wet moisturizing, antibacterial or carrying medicine, and human motion can not be changed to the drawing-off of wound or scar generation, the physical stimulation of compression For it is a kind of stress activity promote the healing of wound or scar.And it is this stress activity to the neoblastic speed of growth, biological living Property foundation and surface wound healing or the reparation etc. of scar it is significant.Therefore, develop it is a kind of have stress activity it is fine The tissue engineering bracket that dimension film is either repaired as in-vivo tissue, or as surface wound or scar nursing all with important Meaning, is also biomaterial Main Trends of The Development.
Many tissues are natural piezoelectrics in human body, such as:Skin, bone, cartilage, tendon, ligament etc., piezo-electric effect comes from Collagen component in tissue, by completing the mutual conversion of mechanical energy and electric energy, can maintain the normal physiological activity of tissue and new Old metabolism, is conducive to the moulding of tissue, reconstruction and function to maintain, and organizes because the polarization charge that piezo-electric effect is produced can promotion organization Growth and healing.This piezo-electric effect be exactly for biology angle it is biological stress activity.Due to the piezoelectricity of tissue I.e. stress key effect of the activity characteristic in tissue reconstruction and wound or scar repair process, will be set for biomaterial Meter provides a kind of new thinking with building.
Kynoar is one of high polymer material with best piezoelectric property, is provided simultaneously with good pliability, can Processability and biocompatibility, the Kynoar with piezoelectric property is compound in existing biomaterial to turn into assign and given birth to The effective ways of thing material piezoelectric property.But Kynoar can obtain α according to the difference of its processing conditions and the process of processing, Can also mutually it be converted in different processing conditions and the process kind of processing between beta, gamma, δ, five kinds of crystalline phases of ε, five kinds of crystalline phases, it is different Crystalline phase there are different characteristics, only β crystalline phases have piezoelectric property, and Kynoar is only in high voltage electric field polarization or machine It can just be obtained under conditions of tool drawing-off.Searching is a kind of can to obtain the Kynoar of β crystalline phases, and the poly- inclined of β crystalline phases can be made again PVF be dispersed in obtained in biomaterial it is a kind of with piezoelectricity stress activity tissue engineering bracket material or wound or Scar repair material and preparation method thereof, the starting point as the present invention.
The content of the invention
For above-mentioned problem, the invention aims to solve existing biomaterial in tissue engineering bracket material And defect present in wound or scar repair material, obtained using Static Spinning Kynoar with piezoelectric property β crystalline phases Polyvinylidene fluoride nanometer fiber, carries out Static Spinning polyvinylidene fluoride and Static Spinning fibroin egg simultaneously in same take-up drums The composite nano fiber of white and medical high polymer synthetic material, obtains being combined with fibroin albumen and medical high polymer synthetic material The tunica fibrosa that stress be active with piezoelectricity work for the IPN non-woven constructions that nanofiber is constituted with polyvinylidene fluoride nanometer fiber, this Plant tunica fibrosa and can be widely applied to tissue engineering bracket material and wound or scar repair material.Realize the technical side of the present invention Case is:
One kind stress activated fibre film, it is described stress activated fibre film be by polyvinylidene fluoride nanometer fiber and composite Nano Fiber is constituted, and composite nano fiber is made up of mass ratio for 1/20~1/1 fibroin albumen and medical high polymer synthetic material, is gathered The mass ratio of vinylidene and medical high polymer synthetic material is 1/99~5/95, composite nano fiber and polyvinylidene fluoride nanometer The tunica fibrosa of fiber formation IPN non-woven constructions, fiber film thickness is 0.1mm-2mm, wherein Kynoar and medical high polymer The mass ratio of synthetic material is 1/99~5/95.
Described fibroin albumen and a diameter of 500nm- of the composite nano fiber of medical high polymer synthetic material 10000nm, a diameter of 100nm-1000nm of polyvinylidene fluoride nanometer fiber.
Described fibroin albumen is to crush the powder shaped fibroin albumen that obtained diameter is less than 500nm after natural silk degumming, or After natural silk degumming, by dissolving, dialysis is freeze-dried obtained fibroin albumen.
Described medical high polymer synthetic material is polyurethane or one or both of polycaprolactone or polyvinyl alcohol Mixture.
It is a kind of stress activated fibre film preparation method, including silk fibroin protein solution or fibroin albumen powder dispersion, doctor With the preparation of high molecular synthetic material solution and Kynoar solution, it is characterised in that:Described one kind stress activated fibre film Preparation method carry out according to the following steps:
A. the silk fibroin protein solution configured or diameter is taken to be less than 500nm fibroin albumens powder dispersion and medical high polymer Synthetic material solution is mixed, and obtains uniform and stable mixed solution liquid or suspension, and sucked the spinning of Static Spinning The mass ratio of liquid pipe, wherein fibroin albumen and medical high polymer synthetic material is 1/20~1/1, fibroin albumen and medical high polymer The total soluble matters mass concentration of synthetic material is 7wt%~15wt%, and it is 7wt%~15wt% polyvinylidene fluorides to take the concentration configured Alkene solution sucks the spinning liquid pipe of another Static Spinning.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform;
C. electro-spinning is standby stress activated fibre film
There are fibroin albumen and medical high polymer synthetic material mixed solution or suspension and Kynoar solution by inhaling The Static Spinning that spinning liquid pipe is respectively placed in the right and left of rotating drum is pushed away in pump, cycle per minute clock~100 of rotating speed 20 of rotating drum Cycle per minute clock, fibroin albumen and medical high polymer synthetic material mixed solution or suspension push away pump speed to introduce 0.2ml/ hours ~4ml/ hours, the high voltage power supply of Static Spinning exported 5kV~30kV voltage, between the nozzle and rotating drum of spinning liquid pipe Distance is 5cm~30cm, can obtain a diameter of 500nm-10000nm composite nano fiber, and Kynoar solution pushes away pump Speed to introduce 0.05ml/ hours~0.5ml/ hours, the high voltage power supply of Static Spinning exports 5kV~30kV voltage, spinning liquid pipe The distance between nozzle and rotating drum be 5cm~30cm, the Kynoar that can obtain a diameter of 100nm-1000nm is received Rice fiber, in the presence of rotary barrel, you can obtain the IPN nonwoven of composite nano fiber and polyvinylidene fluoride nanometer fiber composition Structure, thickness for 0.1mm-2mm stress activated fibre film, wherein Kynoar and medical high polymer synthetic material quality Than for 1/99~5/95.
Due to use above technical scheme, the present invention stress activated fibre film stress activity power can easily pass through Adjustment stress in activated fibre film Kynoar and medical high polymer synthetic material mass ratio, in mass ratio 1/99~5/95 Between, mass ratio is higher, stress activated fibre film stress activity it is stronger, stress in activated fibre film Kynoar with it is medical The change of the mass ratio (1/99~5/95) of high molecular synthetic material is by fibroin albumen and medical high polymer synthetic material Total soluble matters mass concentration (7wt%~15wt%) is combined with Kynoar solution concentration (7wt%~15wt%) and they are each From the speed to introduce of Static Spinning (pump that pushes away of fibroin albumen and medical high polymer synthetic material mixed solution or suspension releases speed Degree 0.2ml/ hours~4ml/ hours, Kynoar solution pushes away pump speed to introduce 0.05ml/ hours~0.5ml/ hours) group Close to realize.
Due to use above technical scheme, the present invention stress activated fibre film use rotating drum for catch tray, Ke Yifang Just adjusted by adjusting the rotary speed of rotating drum stress activated fibre film fiber-wall-element model structure, rotary speed gets over Height, stress activated fibre film fiber-wall-element model degree it is higher.
Due to use above technical scheme, the present invention stress activated fibre film be used in in-vivo tissue reparation organizational project Biocompatibility, mechanical strength and the requirement slowly degraded of cell tactophily are met during support, the sky of cell growth is provided Gap structure;Be used in and surface wound or scar nursing when meet surface of a wound moisture-absorbing moisture-keeping, it is antibacterial or carry medicine function, together When, the physical stimulation such as compression, drawing-off that can produce human motion to tunica fibrosa is converted to polarization charge by piezo-electric effect, polarization Electric charge will promote the wound healing of growth of new tissue and wound or scar, promote foundation and and the matrix of cambium biological function Between function coordination.
In tunica fibrosa of the present invention stress active material be polyvinylidene fluoride nanometer fiber, polyvinylidene fluoride nanometer fiber has Good piezo-electric effect and biocompatibility, natural material fibroin albumen further improve and ensure that Fibre Membrane Bio is compatible Property, particularly fibroin powder remains the matrix condition of natural biologic material cell development,
The present invention stress activated fibre film, using fibroin albumen composite medical high molecular synthetic material as material, medical height Molecule synthesis material provides and remains its original high intensity and toughness, for stress activated fibre film stable mechanics is provided The guarantee of performance;Stress activated fibre film the woven pore structure of Static Spinning nonwoven, the size of its mesopore can be convenient Realized by the adjustment of spinning technique.The present invention stress activated fibre membrane preparation method be simple and convenient to operate, cost it is low It is honest and clean, there is good controllability to preparation process, present invention pressure stress activated fibre film can be widely applicable to internal tissue work Engineering support material or wound or scar repair material.
Brief description of the drawings
Fig. 1 is stress activated fibre environmental microbes electron microscope.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
See accompanying drawing.
One kind stress activated fibre film, it is described stress activated fibre film be by polyvinylidene fluoride nanometer fiber and composite Nano Fiber is constituted, and composite nano fiber is made up of mass ratio for 1/20~1/1 fibroin albumen and medical high polymer synthetic material, is gathered The mass ratio of vinylidene and medical high polymer synthetic material is 1/99~5/95, composite nano fiber and polyvinylidene fluoride nanometer The tunica fibrosa of fiber formation IPN non-woven constructions, fiber film thickness is 0.1mm-2mm, wherein Kynoar and medical high polymer The mass ratio of synthetic material is 1/99~5/95.
Described fibroin albumen and a diameter of 500nm- of the composite nano fiber of medical high polymer synthetic material 10000nm, a diameter of 100nm-1000nm. of polyvinylidene fluoride nanometer fiber
Described fibroin albumen is to crush the powder shaped fibroin albumen that obtained diameter is less than 500nm after natural silk degumming, or After natural silk degumming, by dissolving, dialysis is freeze-dried obtained fibroin albumen.
Described medical high polymer synthetic material is polyurethane or one or both of polycaprolactone or polyvinyl alcohol Mixture.
It is a kind of stress activated fibre film preparation method, including silk fibroin protein solution or fibroin albumen powder dispersion, doctor With the preparation of high molecular synthetic material solution and Kynoar solution, it is characterised in that:Described one kind stress activated fibre film Preparation method carry out according to the following steps:
A. the silk fibroin protein solution configured or diameter is taken to be less than 500nm fibroin albumens powder dispersion and medical high polymer Synthetic material solution is mixed, and obtains uniform and stable mixed solution liquid or suspension, and sucked the spinning of Static Spinning The mass ratio of liquid pipe, wherein fibroin albumen and medical high polymer synthetic material is 1/20~1/1, fibroin albumen and medical high polymer The total soluble matters mass concentration of synthetic material is 7wt%~15wt%, and it is 7wt%~15wt% polyvinylidene fluorides to take the concentration configured Alkene solution sucks the spinning liquid pipe of another Static Spinning.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform.
C. electro-spinning is standby stress activated fibre film
There are fibroin albumen and medical high polymer synthetic material mixed solution or suspension and Kynoar solution by inhaling The Static Spinning that spinning liquid pipe is respectively placed in the right and left of rotating drum is pushed away in pump, cycle per minute clock~100 of rotating speed 20 of rotating drum Cycle per minute clock, fibroin albumen and medical high polymer synthetic material mixed solution or suspension push away pump speed to introduce 0.2ml/ hours ~4ml/ hours, the high voltage power supply of Static Spinning exported 5kV~30kV voltage, between the nozzle and rotating drum of spinning liquid pipe Distance is 5cm~30cm, can obtain a diameter of 500nm-10000nm composite nano fiber, and Kynoar solution pushes away pump Speed to introduce 0.05ml/ hours~0.5ml/ hours, the high voltage power supply of Static Spinning exports 5kV~30kV voltage, spinning liquid pipe The distance between nozzle and rotating drum be 5cm~30cm, the Kynoar that can obtain a diameter of 100nm-1000nm is received Rice fiber, in the presence of rotary barrel, you can obtain the IPN nonwoven of composite nano fiber and polyvinylidene fluoride nanometer fiber composition Structure, thickness for 0.1mm-2mm stress activated fibre film, wherein Kynoar and medical high polymer synthetic material quality Than for 1/99~5/95.
Silk fibroin protein solution or fibroin albumen powder dispersion in preparation process a as described above, are after natural silk degumming, to pass through Dissolving is crossed, is dialysed, obtained fibroin albumen is freeze-dried and spills into solvent, magnetic stirring is until be completely dissolved the fibroin stablized Crush obtained powder shaped fibroin albumen of the diameter less than 500nm after protein solution, or natural silk degumming to be scattered in solvent, ultrasound The scattered dispersion liquid for obtaining fibroin powder, the mass concentration of silk fibroin protein solution is 5wt%~20wt%;The fibroin egg of dispersion liquid The mass concentration of white powder body is 5wt%~20wt%;The solvent for configuring silk fibroin protein solution is hexafluoroisopropanol or water, and in room The lower magnetic stirring of temperature;Prepare fibroin powder dispersion liquid, medical high polymer synthetic material polyurethane (PU) or polycaprolactone (PCL) or The solvent of polyurethane (PU) and the mixed solution of polycaprolactone (PCL) is DMF or dimethyl acetamide or two Any one in methyl sulfoxide or two kinds of mixture, at normal temperatures magnetic stirring;Prepare medical high polymer synthetic material polyethylene Using water as solvent during alcohol (PVA) solution, and magnetic is stirred at 80 DEG C;The aqueous solution of silk fibroin protein solution can only be with medical high polymer The aqueous solution mixing of synthetic material polyvinyl alcohol (PVA);The hexafluoroisopropanol solution of silk fibroin protein solution can be with medical high score The organic solution that sub- synthetic material polyurethane (PU) or polycaprolactone (PCL) or polyurethane (PU) are mixed with polycaprolactone (PCL) Mixing.
In preparation process c as described above, what is obtained stress Kynoar and medical high polymer in activated fibre film The mass ratio of synthetic material is dense by the total soluble matters quality of fibroin albumen and medical high polymer synthetic material for 1/99~5/95 Degree (7wt%~15wt%) is combined with Kynoar solution concentration (7wt%~15wt%) and their own Static Spinning (fibroin albumen and medical high polymer synthetic material mixed solution or suspension push away pump speed to introduce 0.2ml/ hours to speed to introduce ~4ml/ hours, Kynoar solution pushes away pump speed to introduce 0.05ml/ hours~0.5ml/ hours) combination realizes.
The solvent for configuring Kynoar solution is DMF or dimethyl acetamide or dimethyl sulfoxide (DMSO) In any one or two kinds mixture, at normal temperatures magnetic stir.
Medical high polymer synthetic material polyurethane can be existing with good biocompatibility, elastomeric polyethers Type polyurethane, PAUR and polycarbonate polyurethane.
After fibroin albumen powder can be for mulberry silk or squeezing natural silk degumming, prepared by the method for mechanical crushing, silk The micro-structural of element does not change with matrix feature;After fibroin albumen can be for mulberry silk or squeezing natural silk degumming, by dissolving, thoroughly Analysis, freeze-drying is obtained.
With reference to embodiment, the invention will be further elaborated:
Embodiment one
A. it is the silk fibroin protein solution that solvent, mass concentration are 5wt% by hexafluoroisopropanol, with DMF It is the mixing of 20% polyurethane (PU) solution for solvent quality concentration, obtains fibroin albumen and medical high polymer synthetic material polyurethane (PU) mass ratio is 1/20, and the total soluble matters mass concentration of fibroin albumen and medical high polymer synthetic material polyurethane (PU) is 7wt% mixed solution, and by mixed solution suck Static Spinning spinning liquid pipe, it is dense by solvent of DMF The Kynoar solution spent for 7wt% sucks the spinning liquid pipe of Static Spinning.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform.
C. electro-spinning is standby stress activated fibre film
There are fibroin albumen and the spinning liquid pipe of polyurethane mixed solution and Kynoar solution to distinguish the suction in a steps It is placed in Static Spinning to push away in pump, the cycle per minute clock of rotating speed 20 of rotating drum, the pump that pushes away of fibroin albumen and polyurethane mixed solution releases speed Degree 4ml/ hour, the high voltage power supply of Static Spinning output 5kV voltage, the distance between the nozzle of spinning liquid pipe and rotating drum are 5cm, can obtain a diameter of 500nm composite nano fiber, and Kynoar solution pushes away pump speed to introduce 0.05ml/ hours, The high voltage power supply of Static Spinning exports 5kV voltage, and the distance between the nozzle and rotating drum of spinning liquid pipe is 5cm, be can obtain A diameter of 100nm polyvinylidene fluoride nanometer fiber, in the presence of rotary barrel, you can obtain composite nano fiber and polyvinylidene fluoride Alkene nanofiber composition IPN non-woven constructions, thickness for 0.1mm stress activated fibre film, wherein Kynoar with it is medical The mass ratio of high molecular synthetic material (polyurethane) is 1/99.
Embodiment two
A. it is the silk fibroin protein solution that solvent, mass concentration are 10wt% by hexafluoroisopropanol, is with dimethyl acetamide Solvent quality concentration mixes for 10wt% polycaprolactones (PCL) solution, obtains fibroin albumen and gathers with medical high polymer synthetic material The mass ratio of caprolactone (PCL) is 1/10, the total soluble matters matter of fibroin albumen and medical high polymer synthetic material polycaprolactone (PCL) Measure concentration be 10wt% mixed solution, and by mixed solution suck Static Spinning spinning liquid pipe, using dimethyl acetamide as Solvent strength sucks the spinning liquid pipe of Static Spinning for 10wt% Kynoar solution.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform.
C. electro-spinning is standby stress activated fibre film
Suction in a steps there are into fibroin albumen and polycaprolactone mixed solution and the spinning liquid pipe point of Kynoar solution It is not placed in Static Spinning to push away in pump, the cycle per minute clock of rotating speed 50 of rotating drum, the pump that pushes away of fibroin albumen and polycaprolactone mixed solution is pushed away Go out speed 2ml/ hours, the high voltage power supply of Static Spinning exports 20kV voltage, between the nozzle and rotating drum of spinning liquid pipe Distance is 10cm, can obtain a diameter of 1000nm composite nano fiber, and Kynoar solution pushes away pump speed to introduce 0.05ml/ hours, the high voltage power supply of Static Spinning exported the distance between 20kV voltage, the nozzle and rotating drum of spinning liquid pipe For 10cm, a diameter of 500nm polyvinylidene fluoride nanometer fiber is can obtain, in the presence of rotary barrel, you can obtain composite Nano The IPN non-woven constructions of fiber and polyvinylidene fluoride nanometer fiber composition, thickness for 1mm stress activated fibre film, wherein poly- inclined The mass ratio of PVF and medical high polymer synthetic material (polycaprolactone) is 2/98.
Embodiment three
A. it is the silk fibroin protein solution that solvent, mass concentration are 20wt% by hexafluoroisopropanol, is molten with dimethyl sulfoxide (DMSO) Agent mass concentration is the polyurethane (PU) and polycaprolactone (PCL) that 15% medical high polymer synthetic material composition mass ratio is 1 ︰ 1 Mixed solution is mixed, and obtains fibroin albumen and medical high polymer synthetic material urethane (PU) and the mixture of polycaprolactone (PCL) Mass ratio be 1/10, fibroin albumen and medical high polymer synthetic material urethane (PU) and the total soluble matters matter of polycaprolactone (PCL) The mixed solution that concentration is 15wt% is measured, and mixed solution is sucked into the spinning liquid pipe of Static Spinning, using dimethyl sulfoxide (DMSO) to be molten Agent concentration sucks the spinning liquid pipe of Static Spinning for 8wt% Kynoar solution.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform.
C. electro-spinning is standby stress activated fibre film
Suction in a steps there are into fibroin albumen, polyurethane (PU) and polycaprolactone (PCL) mixed solution and Kynoar The spinning liquid pipe of solution is respectively placed in Static Spinning and pushed away in pump, the cycle per minute clock of rotating speed 100 of rotating drum, fibroin albumen, polyurethane (PU) pump speed to introduce is pushed away 0.2ml/ hour with polycaprolactone (PCL) mixed solution, the high voltage power supply of Static Spinning exports 30kV Voltage, the distance between the nozzle of spinning liquid pipe and rotating drum are 20cm, can obtain a diameter of 10000nm composite Nano Fiber, Kynoar solution pushes away pump speed to introduce 0.05ml/ hours, and the high voltage power supply of Static Spinning exports 20kV voltage, The distance between nozzle and rotating drum of spinning liquid pipe are 20cm, and the polyvinylidene fluoride nanometer that can obtain a diameter of 1000nm is fine Dimension, in the presence of rotary barrel, you can composite nano fiber and polyvinylidene fluoride nanometer fiber composition IPN non-woven constructions, Thickness stress activated fibre film, wherein Kynoar and medical high polymer synthetic material (polyurethane and polycaprolactone for 2mm's Gross mass) mass ratio be 5/95.
Example IV
A. it is the fibroin albumen powder dispersion that solvent, mass concentration are 20% by water, and using water as solvent, mass concentration Mixed for 10% medical high polymer synthetic material polyvinyl alcohol (PVA) solution, obtain fibroin albumen powder and medical high polymer The mass ratio of synthetic material polyvinyl alcohol (PVA) is 1/2, fibroin albumen and medical high polymer synthetic material polyvinyl alcohol (PVA) Total soluble matters mass concentration be 15% mixed solution, and by mixed solution suck Static Spinning spinning liquid pipe, with dimethyl Sulfoxide is the spinning liquid pipe that the Kynoar solution that solvent strength is 15wt% sucks Static Spinning.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform.
C. electro-spinning is standby stress activated fibre film
By the suction in a steps have fibroin albumen and medical high polymer synthetic material polyvinyl alcohol (PVA) mixed solution and The spinning liquid pipe of Kynoar solution is respectively placed in Static Spinning and pushed away in pump, the cycle per minute clock of rotating speed 60 of rotating drum, fibroin albumen Pump speed to introduce is pushed away with the mixed solution of medical high polymer synthetic material polyvinyl alcohol (PVA) 4ml/ hours, the height of Static Spinning Voltage source exports 30kV voltage, and the nozzle of spinning liquid pipe is 30cm with collecting the distance between wheel, be can obtain a diameter of 8000nm composite nano fiber, Kynoar solution pushes away pump speed to introduce 0.07ml/ hours, the high voltage power supply of Static Spinning Export 30kV voltage, the distance between the nozzle of spinning liquid pipe and rotating drum are 30cm, can obtain the poly- of a diameter of 700nm Vinylidene nanofiber, in the presence of rotary barrel, you can obtain composite nano fiber and polyvinylidene fluoride nanometer fiber composition IPN non-woven constructions, thickness stress activated fibre film, wherein Kynoar and medical high polymer synthetic material for 1.5mm's The mass ratio of (polyvinyl alcohol) is 5/95.
Embodiment five
A. be the fibroin albumen powder dispersion that dispersant, mass concentration are 15% by DMF, with DMF is solvent, and mass concentration mixes for 20% medical high polymer synthetic material polyurethane (PU) solution, The mass ratio for obtaining fibroin albumen powder and medical high polymer synthetic material polyurethane (PU) is 1/1, fibroin albumen powder and doctor With the mixed solution that the total soluble matters mass concentration of high molecular synthetic material polyurethane (PU) is 18%, and mixed solution sucked quiet The spinning liquid pipe of electrospinning, using DMF as solvent, concentration sucks electrostatic for 8wt% Kynoar solution The spinning liquid pipe of spinning.
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply The right and left of rotating drum is respectively placed in, is placed in moving back and forth on platform.
C. electro-spinning is standby stress activated fibre film
The mixed solution for having fibroin albumen powder and medical high polymer synthetic material polyurethane (PU) will be inhaled in a steps and is gathered The spinning liquid pipe of vinylidene solution is respectively placed in Static Spinning and pushed away in pump, the cycle per minute clock of rotating speed 80 of rotating drum, electrostatic spinning liquid Speed to introduce 2ml/ hours, the high voltage power supply of Static Spinning exports 25kV voltage, between the nozzle and collection wheel of spinning liquid pipe Distance is 10cm, can obtain a diameter of 5000nm composite nano fiber, and Kynoar solution pushes away pump speed to introduce 0.5ml/ hours, the high voltage power supply of Static Spinning exported the distance between 20kV voltage, the nozzle and rotating drum of spinning liquid pipe For 10cm, a diameter of 300nm polyvinylidene fluoride nanometer fiber is can obtain, in the presence of rotary barrel, you can obtain composite Nano The IPN non-woven constructions of fiber and polyvinylidene fluoride nanometer fiber composition, thickness for 1mm stress activated fibre film, wherein poly- inclined The mass ratio of PVF and medical high polymer synthetic material (polyurethane) is 4/95.

Claims (5)

1. one kind stress activated fibre film, it is characterised in that:It is described stress activated fibre film be by polyvinylidene fluoride nanometer fiber Constituted with composite nano fiber, composite nano fiber is synthesized by mass ratio for 1/20~1/1 fibroin albumen and medical high polymer Material is constituted, and the mass ratio of Kynoar and medical high polymer synthetic material is 1/99~5/95, and composite nano fiber is with gathering The tunica fibrosa of vinylidene nanofiber formation IPN non-woven constructions, fiber film thickness is 0.1mm-2mm.
2. one kind according to claim 1 stress activated fibre film, it is characterised in that:Described composite nano fiber it is straight Footpath is 500nm-10000nm, a diameter of 100nm-1000nm of polyvinylidene fluoride nanometer fiber.
3. one kind according to claim 1 stress activated fibre film, it is characterised in that:Described fibroin albumen is de- for silk Crush obtained diameter after glue to be less than after 500nm powder shaped fibroin albumen or natural silk degumming, by dissolving, dialysis, freezing is dry Dry obtained fibroin albumen.
4. one kind according to claim 1 stress activated fibre film, it is characterised in that:Described medical high polymer synthesis material Expect the mixture for polyurethane or one or both of polycaprolactone or polyvinyl alcohol.
5. it is a kind of stress activated fibre film preparation method, it is including silk fibroin protein solution or fibroin albumen powder dispersion, medical The preparation of high molecular synthetic material solution and Kynoar solution, it is characterised in that:It is described stress activated fibre film preparation Method is carried out according to the following steps:
A. the silk fibroin protein solution configured or diameter is taken to be synthesized less than 500nm fibroin albumen powder dispersions with medical high polymer Material solution is mixed, and obtains uniform and stable mixed solution or suspension, and is sucked the spinning liquid pipe of Static Spinning, its The mass ratio of middle fibroin albumen and medical high polymer synthetic material is 1/20~1/1, and fibroin albumen synthesizes material with medical high polymer The total soluble matters mass concentration of material is 7wt%~15wt%, and it is 7wt%~15wt% Kynoar solutions to take the concentration configured Suck the spinning liquid pipe of another Static Spinning;
B. the device of Static Spinning is built, using rotating drum as catch tray, two sets of Static Spinnings push away pump and corresponding high voltage power supply difference The right and left of rotating drum is positioned over, is placed in moving back and forth on platform;
C. electro-spinning is standby stress activated fibre film
There are fibroin albumen and the spinning of medical high polymer synthetic material mixed solution or suspension and Kynoar solution by inhaling The Static Spinning that liquid pipe is respectively placed in the right and left of rotating drum is pushed away in pump, and cycle per minute clock~100 week of rotating speed 20 of rotating drum/ Minute, fibroin albumen and medical high polymer synthetic material mixed solution or suspension push away pump speed to introduce 0.2ml/ hours~ 4ml/ hours, the high voltage power supply of Static Spinning exported 5kV~30kV voltage, between the nozzle and rotating drum of spinning liquid pipe away from From for 5cm~30cm, a diameter of 500nm-10000nm composite nano fiber is can obtain, the pump that pushes away of Kynoar solution is pushed away Go out speed 0.05ml/ hours~0.5ml/ hours, the high voltage power supply of Static Spinning exports 5kV~30kV voltage, spinning liquid pipe The distance between nozzle and rotating drum are 5cm~30cm, can obtain a diameter of 100nm-1000nm polyvinylidene fluoride nanometer Fiber, in the presence of rotary barrel, you can obtain the IPN nonwoven knot of composite nano fiber and polyvinylidene fluoride nanometer fiber composition Structure, thickness for 0.1mm-2mm stress activated fibre film, wherein Kynoar and medical high polymer synthetic material mass ratio For 1/99~5/95.
CN201710409812.5A 2017-06-02 2017-06-02 One kind stress activated fibre film and preparation method thereof Pending CN107158475A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710409812.5A CN107158475A (en) 2017-06-02 2017-06-02 One kind stress activated fibre film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710409812.5A CN107158475A (en) 2017-06-02 2017-06-02 One kind stress activated fibre film and preparation method thereof

Publications (1)

Publication Number Publication Date
CN107158475A true CN107158475A (en) 2017-09-15

Family

ID=59824318

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710409812.5A Pending CN107158475A (en) 2017-06-02 2017-06-02 One kind stress activated fibre film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107158475A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110694115A (en) * 2019-10-22 2020-01-17 上海交通大学医学院附属第九人民医院 Method for constructing tendon tissue in vitro, and biological material and application thereof
CN112999431A (en) * 2021-02-08 2021-06-22 东华大学 Self-driven piezoelectric response surface hydrophilicity and hydrophobicity regulating intravascular stent and preparation method thereof
CN113117150A (en) * 2019-12-31 2021-07-16 广州迈普再生医学科技股份有限公司 Guided tissue regeneration membrane and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103768959A (en) * 2014-01-26 2014-05-07 中国科学院重庆绿色智能技术研究院 Hydrophilic and hydrophobic interpenetrating polymer network nanofiber, forward osmosis membrane and preparation method
CN106390197A (en) * 2016-11-02 2017-02-15 武汉纺织大学 Stress active tissue engineering scaffold material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103768959A (en) * 2014-01-26 2014-05-07 中国科学院重庆绿色智能技术研究院 Hydrophilic and hydrophobic interpenetrating polymer network nanofiber, forward osmosis membrane and preparation method
CN106390197A (en) * 2016-11-02 2017-02-15 武汉纺织大学 Stress active tissue engineering scaffold material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110694115A (en) * 2019-10-22 2020-01-17 上海交通大学医学院附属第九人民医院 Method for constructing tendon tissue in vitro, and biological material and application thereof
CN110694115B (en) * 2019-10-22 2022-03-01 上海交通大学医学院附属第九人民医院 Method for constructing tendon tissue in vitro, and biological material and application thereof
CN113117150A (en) * 2019-12-31 2021-07-16 广州迈普再生医学科技股份有限公司 Guided tissue regeneration membrane and preparation method and application thereof
CN113117150B (en) * 2019-12-31 2022-07-19 广州迈普再生医学科技股份有限公司 Guided tissue regeneration membrane and preparation method and application thereof
CN112999431A (en) * 2021-02-08 2021-06-22 东华大学 Self-driven piezoelectric response surface hydrophilicity and hydrophobicity regulating intravascular stent and preparation method thereof
CN112999431B (en) * 2021-02-08 2021-11-19 东华大学 Self-driven piezoelectric response surface hydrophilicity and hydrophobicity regulating intravascular stent and preparation method thereof

Similar Documents

Publication Publication Date Title
Shang et al. Spinning and applications of bioinspired fiber systems
Zhang et al. Electroactive electrospun nanofibers for tissue engineering
MacIntosh et al. Skeletal tissue engineering using silk biomaterials
CN101502671B (en) Method for preparing silk fibroin/ P(LLA-CL) compound nano fiber structure repair stand
CN102886063B (en) Preparation and application of cellulose nanocrystals (CNCs)-reinforced collagen compound substrate
CN101736430B (en) Method for preparing silk fibroin nano-fibre with skin-care effect
CN107158475A (en) One kind stress activated fibre film and preparation method thereof
CN106581779A (en) Skin burn repair material and preparing method thereof
Wei et al. Conductive fibers for biomedical applications
CN101445971A (en) Method for preparing bionic extracellular matrix silk fibroin/chitosan composite nanometer fibre
CN113786516B (en) PCL/Col/MC gradient three-layer artificial periosteum and preparation method and application thereof
CN104043148B (en) A kind of tough belt supporting frame and preparation method thereof
CN106039402A (en) Double-layer periosteum-imitation material and preparation method thereof
CN107648669A (en) The method for building study of vascularized tissue engineering bone film
Ali et al. Biodegradable piezoelectric polymers: recent advancements in materials and applications
CN102166372B (en) Manufacturing method of composite nanofiber scaffold for promoting repair of bone defect
CN102091353A (en) Preparation method of controlled-release oriented nanofiber nerve conduit
CN101417150B (en) Preparation method of aliphatic polyester-chitosan composite fiber tissue repair bracket
CN107213505A (en) It is a kind of to suppress γ polyglutamic acids and Hyaluronan fibers wound dressing of cicatrization and preparation method thereof
CN107737364A (en) A kind of wound dressing and preparation method thereof
CN103127553A (en) Preparation method of nano micrometer structure coexistence chitosan double-layer support
CN106390197B (en) One kind stress active mass's engineering scaffold material and preparation method thereof
CN110354307A (en) Based on the albumen sericin gel and its preparation method and application for turning vectors containing human platelet-derived growth gene silk
CN103861145A (en) Immediately crosslinking technology for preparing macroporous three-dimensional nanofiber bracket
Meng et al. Recent advances of electrospun nanofiber-enhanced hydrogel composite scaffolds in tissue engineering

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170915

WD01 Invention patent application deemed withdrawn after publication