CN104963025A - Coaxial electrospinning process of fibroin-polycaprolactone bi-component ultrafine fiber - Google Patents
Coaxial electrospinning process of fibroin-polycaprolactone bi-component ultrafine fiber Download PDFInfo
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Abstract
The invention discloses a coaxial electrospinning process of a fibroin-polycaprolactone bi-component ultrafine fiber. By optimizing the inner layer polycaprolactone solution concentration and the solvent component proportion, an inner layer polycaprolactone spinning solution and an outer layer fibroin spinning solution almost volatilize synchronously in a synchronous stretching process, and the incidence rate of coating rate decline caused by outer layer breakage due to earlier stretch stop than the inner layer can be reduced. The process provided by the invention employs the laboratory optimized concentration parameters corresponding to the inner layer solution and the outer layer solution, makes preliminary adjustment for almost synchronous volatilization of the inner layer and the outer layer, then adjusts the dosage of the dichloromethane solvent in the mixed solvent of the inner layer solution to regulate the solvent volatilization speed of the inner layer solution, and makes second fine adjustment for almost synchronous volatilization of the inner layer and the outer layer. The process provided by the invention has the advantages of simple operation method and easy realization, greatly improves the coating rate of the fibroin-polycaprolactone bi-component ultrafine fiber, and increases the stability of the fiber during application in bionic engineering.
Description
Technical field
The present invention relates to a kind of electrostatic spinning process, be specifically related to a kind of coaxial electrostatic spinning technique.
Background technology
Adopt organizational engineering to be built with bioactive planting body in vitro, and implant that to substitute and repair human lesion, the tissue of defect and organ be one of forward position study hotspot that materialogy, engineering science and life science are common instantly.Wherein tissue engineering bracket is the basic boom of engineered tissue, should possess structure and the biological function of natural extracellular matrix, adhere to, grow and propagation, and degradation rate will match with regeneration with supportint cell.From biological viewpoint, the tissue of human body and organ nearly all have form and the structure of nanofiber.Therefore, bionical tissue engineering bracket should be built by nanofiber and design, thus imitates extracellular matrix ECM structure to greatest extent, makes support possess biological function, realizes fully integrated with injected organism tissue.In the middle of numerous nanofiber preparation methods, electrostatic spinning technique is one of the simplest and the most direct effective method.The three-dimensional rack adopting method of electrostatic spinning to prepare has very high specific surface area and porosity, the microstructure similar to natural extracellular matrix.The specific area that support is higher is conducive to cell adherence, propagation and differentiation, effectively discharges active factors; Suitable aperture and high porosity are conducive to the formation of cell seeding and extracellular matrix, the transmission of oxygen and nutriment, the discharge etc. of metabolin.
Traditional electrostatic spinning is only applicable to the spinning of one-component or intermingling material.The nanofiber of one-component has the various performances needed for tissue engineering bracket seldom simultaneously, and the advantage of each material can not give full play of by simple physical blending.Therefore, the nanofiber of core-shell structure compound is adopted to have more advantage on material than the nanofiber of one pack system and blending structure.By core-shell structure compound, make fiber have the mechanical performance of sandwich layer and the biocompatibility performance of shell simultaneously, be more suitable for the regulation and control of timbering material performance.Coaxial electrostatic spinning method prepares a kind of comparatively simple and effective method of core shell structure micro nanometer fiber.
Coaxial electrostatic spinning technology is development evolvement on the basis of conventional electrostatic spinning, substantially identical with the principle that conventional electrostatic list spins, and coaxial electrically spun has two cover liquid-supplying systems and inside and outside coaxial nozzle design.According to the needs becoming silk, coaxial electrically spun can select two kinds of different spinning solutions to be extruded by nozzle simultaneously, form the compound drop of outer solution wrapping inner layer solution, then in high-voltage electrostatic field, stretching action is subject to, form compound taylor cone, and then forming superfine skin-core structure jet, jet is outer successively to volatilize with the solvent of internal layer solution, on gathering-device, finally just can obtain the composite nano fiber with core-shell structure.Owing to being distinct before being extruded to nozzle at two kinds of solution, so coaxial electrically spun can design different ectonexine solution by the different liquid feed device of two covers, prepare the composite micro-nano rice fiber with certain structure and specific function.It by the core of bioactie agent load at core-case fibre, can control its diffusion by shell, thus obtains metastable release performance; Also by the design of core shell selection, the advantage performance of each material of core shell can be integrated, makes fiber better be applied to tissue engineering bracket, the mechanical performance of such as sandwich layer, the biocompatibility of shell.
By to the known main cause causing core shell structure to destroy of the process analysis procedure analysis of coaxial electrostatic spinning being: coaxial electrostatic spinning two overlaps liquid-supplying system and two kinds of high polymeric solutions are squeezed to inside and outside coaxial spinning head with different liquid supply rates, forms the compound drop of outer solution wrapping inner layer solution simultaneously.In the electrostatic field formed by high-pressure electrostatic, a large amount of electric charge is gathered rapidly on compound drop surface, be subject to the stretching action of electric field force, the surface tension overcoming drop and internal viscosity power and form inside and outside coaxial compound taylor cone, and then form the coaxial jet of skin-core structure.Jet is constantly refinement in the electric field, and solvent evaporates, and on gathering-device, finally obtain the fiber of core shell structure.In the process of spinning, coaxial jet is sprayed by taylor cone, first through one section of rectilinear motion, i.e. in the initial motion stage of injection stream, then follows spiral motion, and be the swing astable stage of injection stream, motion mode is very complicated.Coaxial electrostatic spinning solution is because the existence of solvent is just at jet surface Accumulating charge.And the concentration of solution is reduced due to the volatilization of solvent, and the electric charge also corresponding minimizing that surface is gathered, and the viscous force of jet and surface tension all can change.When solvent evaporates to a certain extent after, the Coulomb repulsion power of jet surface is not more than viscous force and the surface tension of jet, now jet no longer drawing-off refinement.Because coaxial jet has inside and outside two layers of solution, the solvent of outer solution first volatilizees, and internal layer solution is due to the coated rear volatilization of outer solution.This just makes the skin of jet first stop drawing-off, and jet internal layer continues drawing-off, thus skin is ruptured under the drawing-off of internal layer, causes fibre core shell structure to destroy.
The clad ratio of fibroin-polycaprolactone bi-component superfine fibre detects and electron spectrum can be adopted quantitatively to detect, owing to containing C, H, O, N element in outer fibroin albumen, and internal layer polycaprolactone only has C, H, O element, therefore can by the percentage composition of N element content in N element in electron excitation power spectrum mensuration coaxial electrically spun net and pure silk element, indirectly estimate the composition on core case fibre surface, how much determine that the carbon of fiber surface has is from fibroin albumen, thus the ratio indirectly shared by estimation core case fibre, i.e. core case fibre clad ratio:
Wherein N
surfacerepresent core case fibre surface nitrogen constituent content; N
sfrepresent content shared by fibroin surface nitrogen element; C
sfrepresent fibroin surface carbon constituent content, C
surfacerepresent core case fibre surface carbon constituent content.
Fibroin under existing technique-polycaprolactone bi-component superfine fibre quantitatively detects through above-mentioned electron spectrum, and clad ratio, generally at 25-30%, adds the rejection probability of human organ, greatly have impact on the stability that composite nano fiber is applied in organizational engineering.
Summary of the invention
The object of the invention is the internal layer solution concentration of coaxial electrostatic spinning technique by optimizing fibroin-polycaprolactone bi-component superfine fibre and the ratio of solvent composition, make basic synchronization volatilization in the process of internal layer polycaprolactone spinning solution and the synchro-draw of outer fibroin spinning solution, reduce because skin stops stretching and the incidence of the clad ratio decline caused of rupturing prior to internal layer.
Further, the present invention adopts inside and outside layer solution after laboratory is optimized with the corresponding concentration parameter of empirical value multiple, to do preliminary adjustment for reaching the volatilization of ectonexine basic synchronization; Again by the amount of dichloromethane solvent in the mixed solvent of adjustment internal layer solution, regulating the solvent evaporates speed of internal layer solution, doing secondary fine setting for reaching the volatilization of ectonexine basic synchronization.
The invention provides a kind of coaxial electrostatic spinning technique adopting preliminary adjustment and secondary fine setting, reach the effect of ectonexine basic synchronization volatilization in coaxial electrostatic spinning, method is simple, easily realize at actual production suede, substantially increase the clad ratio of fibroin-polycaprolactone bi-component superfine fibre that the present invention exemplifies, add the stability that it applies in biomimetic engineering.
The invention discloses the coaxial electrostatic spinning technique of a kind of fibroin-polycaprolactone bi-component superfine fibre, comprise the following steps:
S1: fibroin membrane is dissolved in hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 7-9%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of above-mentioned fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 3: 1-5: 1;
S3: with fibroin spinning solution for outer tube spinning solution, polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2 millimeters, and internal diameter is 0.8 millimeter, and inner capillary tube external diameter is 0.7 millimeter, and internal diameter is 0.37 millimeter; Outer tube fltting speed be 1.8 milliliters per hour, the fltting speed of interior pipe be 0.6 milliliter per hour, receiving range is 9-15 centimetre, and voltage-regulation is to 9-18kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
In some embodiments, in S1, fibroin membrane is the high-purity fibroin membrane after the dialysis of silkworm stripping is purified, its preparation process comprises the following steps, silkworm raw silk is come unstuck 2-5 time at 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration, each 30 minutes, deionized water is adopted to wash after coming unstuck 2-5 time, at the oven drying 1-3.5h of 45-60 DEG C after drawing pine, make crin fibroin, the lithium-bromide solution of 100ml 9.3mol/L is joined again by every 15g crin fibroin, crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide, again the mixed solution deionized water dialysis of fibroin and lithium bromide is obtained high-purity silk fibroin protein solution, high-purity silk fibroin protein solution to be placed in polyethylene pan dry 1-3.5h at 12-32 DEG C, make high-purity fibroin membrane.Adopt gentle processing mode, ensure that fibroin albumen can not sex change, adopt dialysis to purify, ensure the purity of raw material.
Detailed description of the invention
Embodiment 1:
The invention discloses the coaxial electrostatic spinning technique of a kind of fibroin-polycaprolactone bi-component superfine fibre, comprise the following steps:
S1: be come unstuck 3 times in 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration by silkworm raw silk, each 30 minutes, then spend deionized water 3 times, obtains crin fibroin after within after drawing pine 3 hours in the baking oven of 55 DEG C, drying;
Join the lithium-bromide solution of 100ml 9.3mol/L according to every 15g fibroin, above-mentioned crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide;
To be placed in polyethylene pan dry 2h at 20 DEG C after the dialysis of the mixed solution deionized water of above-mentioned fibroin and lithium bromide is obtained high-purity silk fibroin protein solution and to make high-purity fibroin membrane;
Above-mentioned high-purity fibroin membrane is dissolved in quantitative hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 9%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of above-mentioned fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 4: 1;
S3: with above-mentioned fibroin spinning solution for outer tube spinning solution, above-mentioned polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2mm, and internal diameter is 0.8mm, and inner capillary tube external diameter is 0.7mm, and internal diameter is 0.37mm; Outer tube fltting speed is 1.8ml/h, and the fltting speed of interior pipe is 0.6ml/h, and receiving range is 12cm, and voltage-regulation is to 20kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
The present embodiment quantitatively detects through electron spectrum, and clad ratio can reach 75.98%.
Also show through SEM ESEM and TEM transmission electron microscope qualitative test, the fibroin after process optimization-polycaprolactone bi-component superfine fibre fibre morphology is better.
Embodiment 2:
The invention discloses the coaxial electrostatic spinning technique of a kind of fibroin-polycaprolactone bi-component superfine fibre, comprise the following steps:
S1: be come unstuck 2 times in 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration by silkworm raw silk, each 30 minutes, then spend deionized water 5 times, obtains crin fibroin after within after drawing pine 0.5 hour in the baking oven of 45 DEG C, drying;
Join the lithium-bromide solution of 100ml 9.3mol/L according to every 15g fibroin, above-mentioned crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide;
To be placed in polyethylene pan dry 4h at 10 DEG C after the dialysis of the mixed solution deionized water of above-mentioned fibroin and lithium bromide is obtained pure silk fibroin protein solution and to make high-purity fibroin membrane;
Above-mentioned high-purity fibroin membrane is dissolved in quantitative hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 6%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of above-mentioned fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 1: 1;
S3: with above-mentioned fibroin spinning solution for outer tube spinning solution, above-mentioned polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2mm, and internal diameter is 0.8mm, and inner capillary tube external diameter is 0.7mm, and internal diameter is 0.37mm; Outer tube fltting speed is 1.8ml/h, and the fltting speed of interior pipe is 0.6ml/h, and receiving range is 8cm, and voltage-regulation is to 8kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
Through the quantitative detection of electron spectrum, the clad ratio of gained fibroin-polycaprolactone bi-component superfine fibre net is 62.73%.
Embodiment 3:
The invention discloses the coaxial electrostatic spinning technique of a kind of fibroin-polycaprolactone bi-component superfine fibre, comprise the following steps;
S1: be come unstuck 5 times in 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration by silkworm raw silk, each 30 minutes, then spend deionized water 2 times, obtains crin fibroin after within after drawing pine 4 hours in the baking oven of 60 DEG C, drying;
Join the lithium-bromide solution of 100ml 9.3mol/L according to every 15g fibroin, above-mentioned crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide;
To be placed in polyethylene pan dry 0.5h at 35 DEG C after the dialysis of the mixed solution deionized water of above-mentioned fibroin and lithium bromide is obtained pure silk fibroin protein solution and to make high-purity fibroin membrane;
Above-mentioned high-purity fibroin membrane is dissolved in quantitative hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 10%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of above-mentioned fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 4: 1;
S3: with above-mentioned fibroin spinning solution for outer tube spinning solution, above-mentioned polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2mm, and internal diameter is 0.8mm, and inner capillary tube external diameter is 0.7mm, and internal diameter is 0.37mm; Outer tube fltting speed is 1.8ml/h, and the fltting speed of interior pipe is 0.6ml/h, and receiving range is 16cm, and voltage-regulation is to 20kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
Through the quantitative detection of electron spectrum, the clad ratio of gained fibroin-polycaprolactone bi-component superfine fibre net is 68.41%.
Embodiment 4:
The invention discloses the coaxial electrostatic spinning technique of a kind of fibroin-polycaprolactone bi-component superfine fibre, comprise the following steps:
S1: be come unstuck 3 times in 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration by silkworm raw silk, each 30 minutes, then spend deionized water 3 times, obtains crin fibroin after within after drawing pine 2 hours in the baking oven of 50 DEG C, drying;
Join the lithium-bromide solution of 100ml 9.3mol/L according to every 15g fibroin, above-mentioned crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide;
To be placed in polyethylene pan dry 1h at 15 DEG C after the dialysis of the mixed solution deionized water of above-mentioned fibroin and lithium bromide is obtained pure silk fibroin protein solution and to make high-purity fibroin membrane;
Above-mentioned high-purity fibroin membrane is dissolved in quantitative hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 9%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of above-mentioned fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 6: 1;
S3: with above-mentioned fibroin spinning solution for outer tube spinning solution, above-mentioned polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2mm, and internal diameter is 0.8mm, and inner capillary tube external diameter is 0.7mm, and internal diameter is 0.37mm; Outer tube fltting speed is 1.8ml/h, and the fltting speed of interior pipe is 0.6ml/h, and receiving range is 12cm, and voltage-regulation is to 18kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
Through the quantitative detection of electron spectrum, the clad ratio of gained fibroin-polycaprolactone bi-component superfine fibre net is 66.43%.
Embodiment 5:
The invention discloses the coaxial electrostatic spinning technique of a kind of fibroin-polycaprolactone bi-component superfine fibre, comprise the following steps:
S1: be come unstuck 4 times in 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration by silkworm raw silk, each 30 minutes, then spend deionized water 4 times, obtains crin fibroin after within after drawing pine 2 hours in the baking oven of 50 DEG C, drying;
Join the lithium-bromide solution of 100ml 9.3mol/L according to every 15g fibroin, above-mentioned crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide;
To be placed in polyethylene pan dry 2.5h at 25 DEG C after the dialysis of the mixed solution deionized water of above-mentioned fibroin and lithium bromide is obtained pure silk fibroin protein solution and to make high-purity fibroin membrane;
Above-mentioned high-purity fibroin membrane is dissolved in quantitative hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 8%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of above-mentioned fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 5: 1;
S3: with above-mentioned fibroin spinning solution for outer tube spinning solution, above-mentioned polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2mm, and internal diameter is 0.8mm, and inner capillary tube external diameter is 0.7mm, and internal diameter is 0.37mm; Outer tube fltting speed is 1.8ml/h, and the fltting speed of interior pipe is 0.6ml/h, and receiving range is 12cm, and voltage-regulation is to 9-18kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
Through the quantitative detection of electron spectrum, the clad ratio of gained fibroin-polycaprolactone bi-component superfine fibre net is 74.61%.
Claims (2)
1. the coaxial electrostatic spinning technique of fibroin-polycaprolactone bi-component superfine fibre, is characterized in that, comprise the following steps:
S1: fibroin membrane is dissolved in hexafluoroisopropanol and forms the fibroin spinning solution that mass fraction is 7-9%;
S2: polycaprolactone is dissolved in the mixed solvent of hexafluoroisopropanol and carrene and forms polycaprolactone spinning solution, the solution's solute mass fraction be made into is 0.56 times of described fibroin spinning solution Solute mass fraction, and in solvent, the volume ratio of hexafluoroisopropanol and carrene is 3: 1-5: 1;
S3: with described fibroin spinning solution for outer tube spinning solution, described polycaprolactone spinning solution is that interior pipe spinning solution carries out coaxial electrostatic spinning, and outer capillary external diameter is 1.2 millimeters, and internal diameter is 0.8 millimeter, inner capillary tube external diameter is 0.7 millimeter, and internal diameter is 0.37 millimeter; Outer tube fltting speed be 1.8 milliliters per hour, the fltting speed of interior pipe be 0.6 milliliter per hour, receiving range is 9-15 centimetre, and voltage-regulation is to 9-18kv, and spinning under room temperature, obtains fibroin-polycaprolactone bi-component superfine fibre net.
2. the coaxial electrostatic spinning technique of fibroin according to claim 1-polycaprolactone bi-component superfine fibre, it is characterized in that, in described S1, fibroin membrane is the high-purity fibroin membrane after the dialysis of silkworm stripping is purified, its preparation process comprises the following steps, silkworm raw silk is come unstuck 2-5 time at 98-100 DEG C in the sodium carbonate liquor of 0.06% in concentration, each 30 minutes, deionized water is adopted to wash after coming unstuck 2-5 time, at the oven drying 1-3.5h of 45-60 DEG C after drawing pine, make crin fibroin, the lithium-bromide solution of 100ml 9.3mol/L is joined again by every 15g crin fibroin, described crin fibroin is dissolved in lithium-bromide solution, form the mixed solution of fibroin and lithium bromide, again the mixed solution deionized water dialysis of fibroin and lithium bromide is obtained high-purity silk fibroin protein solution, described high-purity silk fibroin protein solution to be positioned in polyethylene pan dry 1-3.5h at 12-32 DEG C, make described high-purity fibroin membrane.
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