Gelatin-based micro nanometer fiber membrane material and its production and use
Technical field
The invention belongs to the non-woven fabrics field in biomaterial, the gelatin based micro-nano that more particularly to prepared by needleless electrospinning is fine
Tie up membrane material and application, and the gelatin-based micro nanometer fiber membrane material preparation method, and for preparing gelatin based micro-nano
The electrostatic spinning machine of fiber film material.
Background technology
In the presence of high voltage electric field, powered polymer solution or molten mass can form a cone, here it is so-called
" taylor cone " (Taylor cone);Continue to increase electric-field intensity, polymer solution or molten mass can spray from " taylor cone "
Go out.Injection stream is shaken in the presence of high voltage electric field, is produced the random coil motion of very high frequency, is caused injection stream quilt
Quick to draw and attenuate, solvent volatilizees rapidly, ultimately forms diameter in the fiber of micro/nano level and is scattered in collection dress in a random way
Put, form micro nanometer fiber film, or on the collection device of movement/rotation, form the micro-nano fibre of certain fiber-wall-element model
Film is tieed up, resulting micro nanometer fiber film is referred to as non-woven fabrics.Electrostatic spinning technique is by Zeleny first
(Phys.Rev.1914.3:69~91) invention, Formhals (US Patant, 1,975,504.1934) applied specially it
Profit.At present, electrostatic spinning technique has been used for every field.As a whole, the research to electrostatic spinning can be divided into two sides
Face:First aspect concentrates on the exploration to electrospun material and spinning product characteristicses purposes, and second aspect is then to focus on pair
Electrostatic spinning apparatus reform in itself and process innovation.For in a first aspect, traditional spinning process is difficult to spin diameter to be less than
500nm fiber;And electrostatic spinning can then spin ultra-fine fiber, diameter most I to 1nm.Due to the Optimality of superfine fibre
Can, people conduct in-depth research to its preparation method, applicable raw materials, properties of product etc..Numerous mutual heaps of micro nanometer fiber
Accumulate into micro nanometer fiber membrane material, this material is from structure, and it has an obvious small-size effect, big specific surface area and
The arrangement effect of supermolecule, many small secondary structures and the structure class of extracellular matrix that non-woven fabrics fiber surface is formed
Seemingly, closer to the physical dimension of organism;From performance, due to its special micro nano structure, therefore non-woven fabrics has
Very strong absorption affinity, good filterability, barrier, cohesive, moisture retention, good biocompatibility and biodegradable
Property.So far, more than 100 kinds macromolecules, which are developed, prepares micro nanometer fiber membrane material.Natural polymer is because in biology
There is bigger advantage than synthesis macromolecule in terms of compatibility and degradability, be more suitable for the application in terms of biologic medical, by
The generally favor of domestic and foreign scholars, gelatin is even more the typical case of good properties in bio-molecules.Gelatin is with the skin of animal, bone
For raw material, it is made by classifying, washing the procedure of leaching, degreasing, neutralization, hydrolysis, filtering, concentration, gel, drying, crushing etc. more than ten,
For a kind of tasteless, translucent, hard thin slice, particle or powder.The main composition of gelatin is identical with amino acid composition and divided
Son amount distribution very wide peptide molecule mixture, molecular weight is typically tens of thousands of to ten tens of thousands of.Because gelatin has good biology
Compatibility, under body temperature degradability, good water solubility;The micro nanometer fiber film prepared simultaneously through electrostatic spinning have with it is thin
The similar structure of extracellular matrix collagen, therefore, has huge application prospect in field of medicaments, can be widely used for hemostatic material
Material, bleeding-stopping dressing, tissue engineering bracket material, teeth repairing material, Thermosensitive Material Used for Controlled Releasing of Medicine, artificial skin material, artificial blood vessel
In terms of material, cartilage repair material, biomembrane material, wound covering material, beauty and health care material.Tens passes are had at present
There are the document and patent of pin electrospinning in gelatin.For second aspect electrostatic spinning apparatus reform in itself and process innovation and
Speech, either R&D institution still produces the enterprise of micro nanometer fiber using electrostatic spinning technique at present, wherein most quiet
Electrospinning and technique are all based on the syringe-type electrostatic spinning apparatus with microprojection systems;At the same time, it is other
Some new-type electrostatic spinning apparatus are developed in succession.However, new needleless electrostatic spinning technique is applied in gelatin
Deng the processing of the micro nanometer fiber membrane material of boiomacromolecule, report yet there are no.
In addition, gelatin electrostatic spinning technique is developed so far, the limitation of the following aspects is still faced.One side,
The gelatin fiber generally existing diameter prepared by prior art relatively thick (typically more than micron order), skewness, moisture resistant
Property is poor, yielding, broken, hygroscopic;It is in colloidal state under second aspect, the aqueous solution normal temperature of pure gelatin, it is difficult to pass through
Syringe-type electrostatic spinning apparatus is spun into micro nanometer fiber, and gelatin is not readily dissolved in organic solvent.At present, a limited number of document
Report all concentrates on some fluorine-containing organic solvents, and such as trifluoroethanol, hexafluoroisopropanol, but this method has solvent
Costliness, organic solvent toxicity is big, and the organic solvent of residual is difficult to clean off completely, (Journal of the shortcomings of difficult solvent recovery
Functional Polymers, 2008,21 (3), 312-316;Journal of Biomedical Materials
Research Part A, 2009,90 (3), 671-679);3rd aspect, syringe needle spinneret is used current electrostatic spinning machine more
Mode, syringe needle is easily blocked and spinning efficiency is low.These all limit the extensive use of gelatin-based micro nanometer fiber film.
Additive etc. is added when the present invention by gelatin and other biomolecule by carrying out blending, and further using crosslinking
Agent carries out Controllable cross-linking, to overcome the defect described in above-mentioned one side;By finding suitable solvent, electrostatic spinning is adjusted
When temperature, humidity overcome the defect described in above-mentioned second aspect of gelatin electrospinning;By using sea whelk formula wire vent mode,
Spring wire vent mode, drum-type wire vent mode, screw wire vent mode, rotary shaft wire vent mode or gear type wire vent mode,
The speed of electrostatic spinning wire vent is can greatly improve, and accomplishes continuous spinning operating to overcome described in above-mentioned 3rd aspect
Defect.By these improvement, the present invention can not only simplify the program, cost-effective of gelatin electrostatic spinning, and can be a large amount of
The gelatin-based micro nanometer fiber membrane material for preparing function admirable.This material can be commonly used to do hemostatic material, hemostasis
It is dressing, tissue engineering bracket material, teeth repairing material, Thermosensitive Material Used for Controlled Releasing of Medicine, artificial skin material, artificial blood vessel material, soft
In terms of bone renovating material, biomembrane material, wound covering material, beauty and health care material.
The content of the invention
An object of the present invention is to provide the gelatin-based micro nanometer fiber membrane material prepared by needleless electrostatic spinning
Material.
The second object of the present invention is to provide the method that needleless electrospinning carries out preparing gelatin-based micro nanometer fiber membrane material.
The third object of the present invention is to provide the purposes of gelatin-based micro nanometer fiber membrane material.
The fourth object of the present invention is to provide the electrostatic spinning machine for preparing gelatin-based micro nanometer fiber membrane material.
The present invention is that micro nanometer fiber membrane material is prepared by main base of gelatin, utilizes sea whelk formula electrostatic spinning machine, bullet
Spring formula electrostatic spinning machine, drum-type electrostatic spinning machine, screw electrostatic spinning machine, rotary shaft electrostatic spinning machine or gear type electrostatic
Spinning-drawing machine carries out the electrostatic co-spun yarn of the solution containing gelatin and the solution containing other biomolecule, or by gelatin solution and its
Electrostatic co-blended spinning is carried out after the mixing such as its biomolecule, quick, convenient, the large-scale electrostatic spinning of gelatin is realized, letter
Just different compositions and various sizes of gelatin-based micro nanometer fiber membrane material are prepared to quick scale, after a series of
Processing, is that the further large-scale popularization practicality of gelatin-based micro nanometer fiber membrane material provides the foundation.
The gelatin-based micro nanometer fiber film of the present invention is prepared by needleless electrostatic spinning, constitutes gelatin-based micro-nano
The composition of the micro nanometer fiber of rice tunica fibrosa is made up of gelatin, other biomolecule, additive, emulsifying agent and medicine;Wherein:
The content of gelatin is 2~98wt% (preferred scope is 30~80wt%), and the content of other biomolecule is (excellent for 2~98wt%
It is 10~50wt% to select scope), the content of additive is 0~40wt% (preferred scope is 1~15wt%), the content of emulsifying agent
For 0~40wt% (preferred scope is 0~8wt%), the content of medicine be 0~40wt% (preferred scope is 0.01~
20wt%);
Or
The composition of micro nanometer fiber of gelatin-based micro nanometer fiber film is constituted respectively by gelatin, additive, emulsifying agent and medicine
Thing is constituted, and is made up of other biomolecule, additive, emulsifying agent and medicine;Wherein by gelatin, additive, emulsifying agent and medicine
The content of gelatin is 2~100wt% (preferred scope is 30~80wt%), the content of additive in the micro nanometer fiber of thing composition
For 0~40wt% (preferred scope is 1~15wt%), the content of emulsifying agent is 0~40wt% (preferred scope is 0~8wt%),
The content of medicine is 0~40wt% (preferred scope is 0.01~20wt%);By other biomolecule, additive, emulsifying agent and
The content of other biomolecule is 2~100wt% (preferred scope is 10~50wt%) in the micro nanometer fiber of medicine composition, is added
Plus the content of agent is 0~40wt% (preferred scope is 1~15wt%), (preferred scope is for 0~40wt% for the content of emulsifying agent
0~8wt%), the content of medicine is 0~40wt% (preferred scope is 0.01~20wt%).
Described gelatin-based micro nanometer fiber film is by the micro-nano of transversely arranged micro nanometer fiber film layer and longitudinal arrangement
Rice fiber film layer, which is alternateed, covers (being bottom i.e. by one layer of transversely arranged micro nanometer fiber film, fold for the composition that is layering
Plus the micro nanometer fiber film layer of one layer of longitudinal arrangement, one layer of transversely arranged micro nanometer fiber film layer is covered again afterwards, with such
Push away, alternately cover, be layering).
Described alternates the gelatin-based micro nanometer fiber film for covering the composition that is layering, the micro-nano fibre of its adjacent layer
Tieing up film layer is made up of the micro nanometer fiber of identical component, or is made up of the micro nanometer fiber of heterogeneity.
The thickness of described gelatin-based micro nanometer fiber film is 50nm~5cm, and preferred scope is 1 μm~3cm.
A diameter of 20nm~100 μm of micro nanometer fiber in described gelatin-based micro nanometer fiber film.
The degree of cross linking of micro nanometer fiber in described gelatin-based nano fibrous membrane is 0<The degree of cross linking≤100%, preferably model
Enclose for 5~80%.
The preparation method of the gelatin-based micro nanometer fiber membrane material of the present invention comprises the following steps:
(1) gelatin is dissolved in solvent, stirring added to after being completely dissolved other biomolecule, additive, emulsifying agent and
Medicine, continues to obtain spinning solution, spinning after stirring (time typically stirred is 0.1~48 hour) to formation homogeneous (uniform) fluid solution
The content of gelatin is 2~98wt% (preferred scope is 30~80wt%) in the solute of liquid, the contents of other biomolecule for 2~
98wt% (preferred scope is 10~50wt%), the content of additive is 0~40wt% (preferred scope is 1~15wt%), breast
The content of agent is 0~40wt% (preferred scope is 0~8wt%), and (preferred scope is for 0~40wt% for the content of medicine
0.01~20wt%);Then spinning solution is loaded into being set (such as 2,4,6,8,10-----) with even number for electrostatic spinning machine respectively
More than two liquid baths in, and the composition composition of the spinning solution loaded in adjacent liquid bath is identical or differ, and prepares to spin
Silk;
Or
Gelatin is dissolved in solvent, stirs to being completely dissolved, obtains gelatin solution;Other biomolecule are dissolved in solvent
In, stir to being completely dissolved, obtain other biomolecule solutions;Then additive, emulsifying agent and medicine are added into gelatin solution
Thing, continues to obtain the spinning containing gelatin after stirring (time typically stirred is 0.1~48 hour) to formation homogeneous (uniform) fluid solution
Silk liquid, additive, emulsifying agent and medicine are added into other biomolecule solutions, and continuing stirring, (time typically stirred is 0.1
~48 hours) obtain the spinning solution containing other biomolecule to after forming homogeneous (uniform) fluid solution;The wherein spinning containing gelatin
The content of gelatin is 2~100wt% (preferred scope is 30~80wt%) in the solute of liquid, the content of additive for 0~
40wt% (preferred scope is 1~15wt%), the content of emulsifying agent is 0~40wt% (preferred scope is 0~8wt%), medicine
Content be 0~40wt% (preferred scope is 0.01~20wt%);Its in the solute of spinning solution containing other biomolecule
The content of its biomolecule is 2~100wt% (preferred scope is 10~50wt%), and the content of additive is (excellent for 0~40wt%
It is 1~15wt% to select scope), the content of emulsifying agent is 0~40wt% (preferred scope is 0~8wt%), and the content of medicine is 0
~40wt% (preferred scope is 0.01~20wt%);Then by the spinning solution containing gelatin and the spinning containing other biomolecule
What silk liquid was loaded into electrostatic spinning machine successively respectively sets the more than two adjacent of (such as 2,4,6,8,10-----) with even number
In liquid bath, prepare spinning;
Described electrostatic spinning machine be sea whelk formula electrostatic spinning machine, spring electrostatic spinning machine, drum-type electrostatic spinning machine,
Screw electrostatic spinning machine, rotary shaft electrostatic spinning machine or gear type electrostatic spinning machine;Electrostatic in described adjacent liquid bath
The spinneret of spinning-drawing machine is one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Spinneret over-over mode place (as shown in Figure 7);Described spinneret is the sea whelk of sea whelk formula electrostatic spinning machine, spring
The spring of electrostatic spinning machine, the roller of drum-type electrostatic spinning machine, the screw rod of screw electrostatic spinning machine, rotary shaft electrostatic spinning
The rotating shaft of machine or the gear of gear type electrostatic spinning machine;
Pass through sea whelk formula electrostatic spinning machine, spring electrostatic spinning machine, drum-type electrostatic spinning machine, screw electrostatic spinning
Machine, rotary shaft electrostatic spinning machine or gear type electrostatic spinning machine carry out electrostatic spinning, roller with surface with aluminium foil or cloth, flat
Plate, sieve band etc. are receiver;Wherein, the condition of spinning is:
A) delivery rate of spinning solution is 0.001~50ml/min;
B) environment temperature is 30~90 DEG C;
C) voltage is 1~200kv;
D) the distance between spinneret and receiver are 3~100cm;
E) rotating speed being pivoted of spinneret is 0.001~100rpm;
F) rotary rpm of roller receiver is 0.001~5000rpm, or the linear velocity of flat board and sieve with receiver is
0.00005~250m/min;
G) the drying air temperature of receiver is 1~100 DEG C;
H) temperature of liquid bath is 30~90 DEG C;
(2) it is made up of what is obtained on the receiver after the completion of step (1) electrostatic spinning alternate micro nanometer fiber in length and breadth
The semi-finished product of gelatin-based micro nanometer fiber membrane material remove and be soaked in containing mass percentage concentration as 0~60% crosslinking agent
In water or it is soaked in ethanol solution and is crosslinked (time typically soaked is 1~168 hour), temperature when being crosslinked is
0~30 DEG C;
Or
By the bright of being made up of alternate micro nanometer fiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
It is 0~60% cross-linking agent aqueous solution institute that the semi-finished product of matrix film micro nanometer fiber membrane material, which are removed and are placed in containing mass percentage concentration,
(the general time being crosslinked was by 1~168 hour) is crosslinked in the steam of volatilization or the steaming that ethanol solution volatilizees is placed in
It is crosslinked in vapour (the general time being crosslinked is 1~168 hour);Temperature when being crosslinked is 15~40 DEG C;
It is washed with deionized after the completion of crosslinking, until making gelatin-based micro nanometer fiber film in the case where using crosslinking agent
Remaining crosslinking agent on the semi-finished product of material is washed completely, is dried;
(3) semi-finished product of the gelatin-based micro nanometer fiber membrane material obtained after step (2) is dried irradiate under ultraviolet light
Or irradiation (time typically irradiated is 0.1~20 hour) carries out sterilization treatment under gamma-rays, thus through needleless electrostatic spinning
Prepare gelatin-based micro nanometer fiber film.
The orientation of micro nanometer fiber in gained gelatin-based micro nanometer fiber membrane material is superimposed in length and breadth, constitutes gelatin-based micro-nano
The composition of the micro nanometer fiber of rice tunica fibrosa is made up of gelatin, other biomolecule, additive, emulsifying agent and medicine;Wherein:
The content of gelatin is 2~98wt% (preferred scope is 30~80wt%), and the content of other biomolecule is (excellent for 2~98wt%
It is 10~50wt% to select scope), the content of additive is 0~40wt% (preferred scope is 1~15wt%), the content of emulsifying agent
For 0~40wt% (preferred scope is 0~8wt%), the content of medicine be 0~40wt% (preferred scope is 0.01~
20wt%);Or constitute gelatin-based micro nanometer fiber film micro nanometer fiber composition respectively by gelatin, additive, emulsifying agent and
Medicine is constituted, and is made up of other biomolecule, additive, emulsifying agent and medicine;Wherein by gelatin, additive, emulsifying agent and
In the micro nanometer fiber of medicine composition the content of gelatin is 2~100wt% (preferred scope is 30~80wt%), and additive contains
Measure as 0~40wt% (preferred scope is 1~15wt%), the content of emulsifying agent be 0~40wt% (preferred scope is 0~
8wt%), the content of medicine is 0~40wt% (preferred scope is 0.01~20wt%);By other biomolecule, additive, breast
In the micro nanometer fiber of agent and medicine composition the content of other biomolecule be 2~100wt% (preferred scope is 10~
50wt%), the content of additive is 0~40wt% (preferred scope is 1~15wt%), and the content of emulsifying agent is 0~40wt%
(preferred scope is 0~8wt%), the content of medicine is 0~40wt% (preferred scope is 0.01~20wt%).
Described other biomolecule are selected from type i collagen, chitosan, chitosan, chitosan oligosaccharide, sodium carboxymethylcellulose, glue
It is former albumen, glycosaminoglycan, alginate, carboxymethyl chitosan, chitosan, bioactive glass nano powder, lecithin, transparent
Matter acid, silk-fibroin, chondroitin sulfate, heparin, nucleic acid, cellulose protein, fibronectin in serum, polypeptide, agar, various Portugals
Glycan, poly butyric valeric acid fat, poly butyric caproic acid fat, polycaprolactone, PGA, polylactide, PLA, poly- pair
Two dislike ketone, polyurethane, polyphosphate, polyoxyethylene, lactide, glycolide, fourth lactide, penta lactide, second lactone, oxirane,
Expoxy propane, polyvinylpyrrolidone, polyvinyl alcohol, ethyl cellulose, noncrystalline cellulose, hydroxymethyl cellulose, ethoxy are fine
Tie up one kind in element, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, starch, hydroxyethyl starch, methyl starch
Or it is several.
Described additive is selected from calcium chloride, glycerine, polyvinyl alcohol, polyethylene glycol, the sub- diamines of ethyl carbonization, dissident's dicyan
Acid esters, nitrine diphenylphosphine, sorbierite, hydroxyapatite, beta-calcium phosphate, potassium titanate crystal whisker, potassium chromate, calcium carbonate, citric acid
One or more in calcium, calcium oxalate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, dimethicone.
Described emulsifying agent is single stearic acid glycerine lipoprotein, the third EtOH Stearic fat, polyglycerol fatty acid fat, sorbierite or told
Temperature.
Described medicine be selected from etamsylate, mupirocin, gentamicin sulphate, with filling in mycin sour sodium, Tinidazole, salt
Sour clindamycin, pseudo-ginseng, indigo naturalis, Japanses beauty-berry powder, Yunnan Baiyao, cattail pollen, Tea Polyphenols, tannin, silver chlorate, nano-titanium oxide, receive
Rice zinc oxide, nano silicon, Nano Silver, berberine, organic acid antiseptic, quaternary ammonium salt, biguanides antiseptic, sulfanilamide (SN) are phonetic
Pyridine, efficiency of the joint sulfonation, Norfloxacin, Ciprofloxacin, Ofloxacin, calcitonin, insulin, fibrin ferment, neural production factor, nerve
Save glycosides fat, it is hydrocortisone, control growth factor, expelling parasite class, anticoagulation class, anti-mycobacteria, antiphlogistic, antibiotic, disease-resistant
Poison, anti-infectious agent, antineoplastic, radioactive ray class medicine, immune class preparation, anodyne, antiallergic, anthelmintic, diuresis class
Preparation, muscle relaxant, sex hormone, antidepression class medicine, antiepileptic, antihypertensive, antiarrhymic, anti-diabetic
One kind or several in medicine, antithyroid drug, antitussive, steroid preparation, contrast agent, astringent, resistance prostatitis class preparation
Kind;Or selected from the active ingredient for being used to treat disease extracted from the one or more in Chinese herbal medicine, Tibetan medicine, anaesthetic, seedling medicine
Extract in one or more.
The number-average molecular weight of described gelatin is 10,000~250,000.
Described gelatin is medical gelatin, edible gelatin or gelatin used for cosmetic.
Described solvent is selected from water, formic acid, acetic acid, hydrochloric acid, salicylic acid, ethanol water, benzene first diacid, urea, thiocarbamide,
One or more in kbr aqueous solution, sodium-chloride water solution, glycerine, dichloromethane and tetrahydrofuran.
The crosslinking agent be selected from glutaraldehyde, carbodiimides, Geniposide, divinylsulfone, formaldehyde, glyoxal, MDA,
Butanedial, hexandial, dialdehyde in heptan, suberic aldehyde, azel aldehyde, decanedial, glucose, dialdehyde glucose, glucan, oxidation grape
One or more in sugar, oxidized dextran, diepoxides, divinylsulfone.
The gelatin-based micro nanometer fiber membrane material of the present invention can be applied to biomedicine, for preparing hemostatic material, hemostasis
It is dressing, tissue engineering bracket material, teeth repairing material, Thermosensitive Material Used for Controlled Releasing of Medicine, artificial skin material, artificial blood vessel material, soft
Bone renovating material, biomembrane material, wound covering material, beauty and health care material etc..
The present invention obtains the gelatin-based micro nanometer fiber membrane material of the different degrees of cross linking by the method for chemical crosslinking.
Sea whelk formula electrostatic spinning machine, the spring provided by the present invention for being used to prepare gelatin-based micro nanometer fiber membrane material
Electrostatic spinning machine, drum-type electrostatic spinning machine, screw electrostatic spinning machine, rotary shaft electrostatic spinning machine or gear type electrostatic spinning
Machine includes:High voltage power supply, liquid bath, receiver, ambient temperature control device, ambient humidity control device, feeding device etc.;It is high
Voltage source uses both positive and negative polarity high direct voltage output voltage, and the ceiling voltage of output is 200kv;Liquid bath is to provide raw material to spinneret
Device, in the case of normal electrostatic spinning, its maximum amount of liquid storage can use roller, flat board, sieve band up to 4L, receiver
Etc. various forms of receivers, it is therefore an objective to realize the continuous collection of gelatin-based micro nanometer fiber membrane material.Meanwhile, can in receiver
Addition solvent recovery unit is reclaimed to solvent used in electrostatic spinning;Ambient temperature control device can use temperature control
Instrument processed, infrared lamp, resistance wire, thermal station convey the device of circulating air and carry out appropriate heating, make temperature control 30~
Between 90 DEG C, precision controlling is in the range of ± 2 DEG C;Ambient humidity control device can be handled using humidity controller,
Control accuracy is in ± 5%RH;Feeding device is fed using gravity or machinery conveying, is equipped with small-sized mixing machine to make input
Spinning solution in liquid bath is uniform, keeps liquid level in liquid bath constant and the concentration of spinning solution in liquid bath is constant;Sea whelk formula Static Spinning
The sea whelk spinneret of silk machine, the spring spinneret of spring electrostatic spinning machine, the drum spinning head of drum-type electrostatic spinning machine, spiral shell
The tooth of the screw spinning head of rod-type electrostatic spinning machine, the rotating shaft spinneret of rotary shaft electrostatic spinning machine or gear type electrostatic spinning machine
Take turns spinneret to prepare from alloys such as stainless steel, copper or iron nickel, by spring, roller, screw rod, rotating shaft, multiple gears or multiple
The spinneret that sea whelk is constituted is uniformly distributed, it is ensured that electrostatic spinning it is uniform quick.
The present invention to existing electrostatic spinning machine and technological parameter by being improved, the biomolecule Static Spinning such as optimization gelatin
The technological parameter of silk, solves the low problem of gelatin electrospinning efficiency.Described sea whelk electrostatic spinning machine, spring electrostatic spinning machine
Structure is similar, and with similar spinneret (as shown in Figure 1);Described sea whelk formula electrostatic spinning machine, spring electrostatic spinning
Machine, drum-type electrostatic spinning machine, screw electrostatic spinning machine, each portion of rotary shaft electrostatic spinning machine or gear type electrostatic spinning machine
Annexation between part is identical, and difference is only the replacing of spinneret, each portion of the various electrostatic spinning machines as shown in Fig. 1~5
Annexation between part.
Sea whelk formula electrostatic spinning machine, the spring provided by the present invention for being used to prepare gelatin-based micro nanometer fiber membrane material
Electrostatic spinning machine, drum-type electrostatic spinning machine, screw electrostatic spinning machine, rotary shaft electrostatic spinning machine or gear type electrostatic spinning
Machine includes:Liquid bath, spinneret, high voltage power supply, insulation board, lowering or hoisting gear, ambient temperature control device (such as temperature controller
Deng), ambient humidity control device (such as humidity controller), receiver, runner, air-heater, hot air duct and rack;
The liquid baths of more than two electrostatic spinning machines is provided with described rack, and (liquid bath can be by polytetrafluoroethylmaterial material
It is processed into), and each described liquid bath is each provided with feed pipe and (can be made up of plastic material, such as pp pipes, pvc pipes
Deng);And the spinneret of the electrostatic spinning machine in the liquid bath of adjacent electrostatic spinning machine is one longitudinal direction side of placement in a liquid bath
To spinneret, the over-over mode that the spinneret of a horizontal direction is placed in a liquid bath places (as shown in Figure 7);
The spinneret of described electrostatic spinning machine is mounted in rotary shaft, and (can be by poly- four by rotary shaft and driving member
PVF is made) be connected, the shaft coupling that described driving member is connected by bevel gear and with bevel gear is constituted, shaft coupling with it is described
Rotary shaft (two sections of rotary shaft can be made up of unlike material) one end connection, bevel gear is connected with the bearing of motor, leads to
The regulation for the rotating speed for crossing the rotating speed of controlled motor to realize spinneret;The other end of described rotary shaft and the positive pole of high voltage power supply
It is connected, introduces high-pressure electrostatic;
The liquid bath of described electrostatic spinning machine, ambient temperature control device (such as temperature controller, infrared lamp, resistance wire,
Thermal station conveys device of circulating air etc., and can realize temperature by adjusting infrared lamp, resistance wire or the power of thermal station
Regulation and control), ambient humidity control device (such as humidity controller) fixed (can be fixed by insulated screw) is arranged on can
Realize on the described insulation board of horizontal lifting, lowering or hoisting gear (such as lifting platform or very heavy is installed below described insulation board
Top), to control the lifting of insulation board;
Described receiver is located at the top of described liquid bath and on the swinging mounting above rack, swinging mounting
It is connected with described runner, runner is installed by U-steel frame and (installation can be fixed with insulated bolt) on rack, rotates
Support is connected with the negative pole of high-pressure electrostatic, so as to form high-voltage electrostatic field between spinneret and receiver;
The belt of motor of the described receiver with being fixed on swinging mounting is connected, belt pulley and belt through motor
It is rotated (rotation of receiver is driven by attached motor);The air inlet of described hot air duct and described outside cabinet
The air outlet of air-heater be connected, the air outlet of hot air duct is located at the top of receiver.
Described liquid bath is respectively by the feed pipe and described outside cabinet setting and described liquid bath number of each self installation
The respective pipeline (can be made up of stainless steel material) of amount identical fluid reservoir is connected correspondingly.
Controlled valve and flowmeter for controlling spinning solution flow is installed on the pipeline of described pipeline, it is quiet to ensure
The height of spinning liquid level in the liquid bath of Electrospun machine.
Described runner can be connected by drive link with the bearing of motor carries out the rotation for automatically controlling runner.
Described spinneret is that the sea whelk of sea whelk formula electrostatic spinning machine, the spring of spring electrostatic spinning machine, drum-type are quiet
Roller, the screw rod of screw electrostatic spinning machine, the rotating shaft of rotary shaft electrostatic spinning machine or the gear type electrostatic spinning of Electrospun machine
The gear of machine.The spinneret being made up of spring, roller, screw rod, rotating shaft, multiple gears or multiple sea whelks is uniformly distributed.For bullet
Spring, roller, screw rod, rotating shaft also may be selected multiple.
The material of described rack can be acrylic glass.
The controlled diameter of the micro nanometer fiber of the gelatin-based micro nanometer fiber membrane material of the present invention, length are controllable, the degree of cross linking
It is controllable.After a receiver has collected gelatin-based micro nanometer fiber membrane material, the runner that can manually or automatically rotate
Rotate, change and continue to collect gelatin-based micro nanometer fiber membrane material for next receiver, thus can continuously prepare gelatin-based micro-
Micro/nano fibrous membrane material.
Present invention employs a series of needleless electrostatic spinning machines, conveniently and efficiently using electrostatic spinning technique, main body is equipped with
Gelatin, other biomolecule, additive, emulsifying agent, crosslinking agent, solvent, have prepared gelatin-based micro nanometer fiber membrane material.Institute
The gelatin-based micro nanometer fiber membrane material of preparation has good biocompatibility, Bioabsorbable, biodegradability, this
Impart the more excellent performance of material.By follow-up processing, can effectively it is practical be applied to hemostatic material, bleeding-stopping dressing,
Tissue engineering bracket material, teeth repairing material, Thermosensitive Material Used for Controlled Releasing of Medicine, artificial skin material, artificial blood vessel material, repair of cartilage
In terms of material, biomembrane material, wound covering material, beauty and health care material.
Brief description of the drawings
The structural representation of Fig. 1 sea whelk formula electrostatic spinning machines and spring electrostatic spinning machine.
The structural representation of Fig. 2 screw electrostatic spinning machines.
The structural representation of Fig. 3 drum-type electrostatic spinning machines.
The structural representation of Fig. 4 rotary shaft electrostatic spinning machines.
The structural representation of Fig. 5 gear type electrostatic spinning machines.
The gelatin based nano-fiber prepared with the gelatin solution that mass concentration is 12% of Fig. 6 embodiment of the present invention 1
The SEM top views of membrane material.
The schematic top plan view of the sea whelk wire device of sea whelk formula electrostatic spinning machine used in Fig. 7 embodiment of the present invention 1.
The sea whelk wire device of sea whelk formula electrostatic spinning machine used and the master of collection device in Fig. 8 embodiment of the present invention 1
Depending on schematic diagram.
Reference
1. the liquid bath of 2. controlled valve of fluid reservoir, 3. flowmeter 4.
5. the lowering or hoisting gear of 6. high voltage power supply of spinneret, 7. insulation board 8.
9. the ambient humidity control device of ambient temperature control device 10.
11. the pipeline of 12. runner of receiver, 13. air-heater 14.
15. the rack of 16. hot air duct of feed pipe 17.
Embodiment
Embodiment 1
As shown in figure 1, the sea whelk formula electrostatic spinning machine for preparing gelatin-based micro nanometer fiber membrane material, it is by Asia
More than two sea whelk formula Static Spinnings being processed into by polytetrafluoroethylmaterial material are installed in the rack 17 of gram force glass preparation
The liquid bath 4 of silk machine, and each described liquid bath is each provided with the feed pipe 15 being made up of pp plastic materials;And it is adjacent
The sea whelk spinneret (being made up of multiple sea whelks) of sea whelk formula electrostatic spinning machine in liquid bath is one longitudinal direction of placement in a liquid bath
The over-over mode that the sea whelk spinneret of a horizontal direction is placed in the sea whelk spinneret in direction, a liquid bath is placed (such as Fig. 7 institutes
Show).
The sea whelk spinneret of described sea whelk formula electrostatic spinning machine is mounted in rotary shaft, and by rotary shaft and by poly- four
The driving member that PVF is made is connected, and the shaft coupling that described driving member is connected by bevel gear and with bevel gear is constituted, shaft coupling
Device is connected with one end of described rotary shaft (two ends of rotary shaft can be made up of polytetrafluoroethylene (PTFE) and stainless steel metal respectively), cone
Gear is connected with the bearing of motor, and the regulation of the rotating speed of spinneret is realized by the rotating speed of controlled motor;Described rotation
The other end of axle is connected with the positive pole of high voltage power supply, introduces high-pressure electrostatic.
The liquid bath 4 of described sea whelk formula electrostatic spinning machine, ambient temperature control device (such as temperature controller) 9, environmental wet
Degree control device (such as humidity controller) 10 be fixedly mounted on by insulated screw can realize it is exhausted as described in horizontal lifting
On listrium 7, the lower section of described insulation board 7 is provided with jack for lowering or hoisting gear 8, to control the lifting of insulation board 7.
Using roller as receiver 11, it is located at the surface of described liquid bath 4 and installed in the rotation branch of the top of rack 17
On frame, swinging mounting is connected (runner 12 can be connected by drive link with the bearing of motor) with runner 12, and runner 12 passes through
U-steel frame installs (installation is fixed with insulated bolt) on rack 17, and swinging mounting is connected with the negative pole of high-pressure electrostatic,
So as to form high-voltage electrostatic field between sea whelk spinneret and roller.
The belt of motor of the described roller with being fixed on swinging mounting is connected, belt pulley and belt band through motor
Dynamic rotation;The air inlet for the hot air duct 16 being connected with the air outlet of the air-heater 13 of the described outside of rack 17 is located at roller
Top.
Described liquid bath 4 is respectively by the feed pipe 15 and set and described liquid outside described rack 17 of each self installation
The respective pipeline 14 being made up of stainless steel material of the quantity identical fluid reservoir 1 of groove 4 is connected correspondingly;And institute
Controlled valve 2 and flowmeter 3 for controlling spinning solution flow is installed, to ensure electrostatic spinning on the pipeline for the pipeline 14 stated
The height of spinning liquid level in the liquid bath of machine.
Gelatin-based micro/nano fibrous membrane material is prepared using above-mentioned sea whelk formula electrostatic spinning machine.
(1) use molecular weight for 50,000 pharmagel, gelatin is soluble in water, and stirring adds collagen to after being completely dissolved
Albumen, continues to stir obtaining the content of gelatin in spinning solution, the solute of spinning solution after homogeneous (uniform) fluid solution and be to being formed for 7 hours
98wt%, the content of collagen is 2wt%;Then spinning solution is loaded into 2 adjacent liquid baths of electrostatic spinning machine respectively
In, and the composition composition of the spinning solution loaded in adjacent liquid bath is identical, prepares spinning;
Described electrostatic spinning machine is sea whelk formula electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode places (as shown in Figure 7);Described spinneret is the sea whelk of sea whelk formula electrostatic spinning machine;
Electrostatic spinning is carried out by sea whelk formula electrostatic spinning machine, is receiver (such as Fig. 8 institutes using roller of the surface with aluminium foil
Show);Wherein, the condition of spinning is:
A) delivery rate of spinning solution is 50ml/h;B) environment temperature is 35 DEG C;C) voltage is 70kv;D) spinneret is with connecing
It is 20cm to receive the distance between device;E) rotating speed being pivoted of spinneret is 10rpm;F) rotary rpm of roller receiver is
50rpm;G) the drying air temperature of receiver is 70 DEG C;H) temperature of liquid bath is 30 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is 50 μm of gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Semi-finished product.The described semi-finished product for alternateing the gelatin-based micro/nano fibrous membrane material for covering the composition that is layering, its adjacent layer
Nanofiber film layer be to be made up of the nanofiber of identical component, the diameter range of nanofiber is 70~220nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based micro/nano fibrous membrane material are removed to be placed in be volatilized containing mass percentage concentration by the 30% Geniposide aqueous solution
Steam in carry out crosslinking 1 hour, temperature when being crosslinked is 35 DEG C;It is washed with deionized after the completion of crosslinking, until making
Remaining Geniposide crosslinking agent on the semi-finished product of gelatin-based micro/nano fibrous membrane material is washed completely, is dried;
(3) semi-finished product of the gelatin-based micro/nano fibrous membrane material obtained after step (2) is dried irradiate 20 under gamma-rays
Hour carries out sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 50 μm through needleless electrostatic spinning
(as shown in Figure 6).The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is
10.3%.
Embodiment 2
As shown in Fig. 2 the structure and reality of the screw electrostatic spinning machine for preparing gelatin-based micro nanometer fiber membrane material
The structure for applying the sea whelk formula electrostatic spinning machine of example 1 is essentially identical, simply changes spinneret, sea whelk spinneret is changed into screw spinning
Head.
Gelatin-based micrometer fibers membrane material is prepared using above-mentioned screw electrostatic spinning machine.
(1) use molecular weight for 250,000 gelatin, gelatin is dissolved in 1wt% acetic acid solutions, stir to after being completely dissolved
Chitosan is added, continues stirring and obtains gelatin in spinning solution, the solute of spinning solution to after forming homogeneous (uniform) fluid solution in 48 hours
Content is 98wt%, and the content of chitosan is 2wt%;Then spinning solution is loaded into respectively 4 of electrostatic spinning machine it is adjacent
In liquid bath, and the composition composition of the spinning solution loaded in adjacent liquid bath is identical, prepares spinning;
Described electrostatic spinning machine is screw electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the screw rod of screw electrostatic spinning machine;
Electrostatic spinning is carried out by screw electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 0.001ml/h;B) environment temperature is 30 DEG C;C) voltage is 30kv;D) spinneret
It is 10cm with the distance between receiver;E) rotating speed being pivoted of spinneret is 0.001rpm;F) rotation of roller receiver
Speed of walking around is 5000rpm;G) the drying air temperature of receiver is 100 DEG C;H) temperature of liquid bath is 90 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged micrometer fibers film layer
It is the half of 5cm gelatin-based micrometer fibers membrane material that the micrometer fibers film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based micrometer fibers membrane material for covering the composition that is layering, its adjacent layer
Micrometer fibers film layer is made up of the micrometer fibers of identical component, and the diameter range of micrometer fibers is 30~100 μm;
(2) by being made up of alternate micrometer fibers in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based micrometer fibers membrane material are removed to be placed in be volatilized containing mass percentage concentration by 60% glutaraldehyde water solution
Steam in carry out crosslinking 168 hours, temperature when being crosslinked is 40 DEG C;It is washed with deionized after the completion of crosslinking, until
Remaining glutaraldehyde cross-linking agent on the semi-finished product of gelatin-based micrometer fibers membrane material is washed completely, is dried;
(3) semi-finished product of the gelatin-based micrometer fibers membrane material obtained after step (2) is dried irradiate 0.1 under ultraviolet light
Hour carries out sterilization treatment, thus prepares the gelatin-based micrometer fibers membrane material that thickness is 5cm through needleless electrostatic spinning.Press
The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micrometer fibers membrane material is 100%.
Embodiment 3
As shown in figure 3, structure and the implementation of drum-type electrostatic spinning machine for preparing gelatin-based micro/nano fibrous membrane material
The structure of the sea whelk formula electrostatic spinning machine of example 1 is essentially identical, simply changes spinneret, sea whelk spinneret is changed into drum spinning
Head.
Gelatin-based micro/nano fibrous membrane material is prepared using above-mentioned drum-type electrostatic spinning machine.
(1) use molecular weight for 10,000 gelatin, gelatin be dissolved in 5wt% ethanol solution, stirring to being completely dissolved,
Obtain gelatin solution;Chitosan is dissolved in 1wt% acetic acid solutions, stirs to being completely dissolved, obtains chitosan solution;Then to
Calcium alginate is added in gelatin solution, continues stirring and obtains the spinning containing gelatin to after forming homogeneous (uniform) fluid solution in 12 hours
Liquid;The content of gelatin is 90wt% wherein in the solute of the spinning solution containing gelatin, and the content of calcium alginate is 10wt%;Shell gathers
The content of chitosan is 100wt% in the solute of sugar juice, and is used as spinning solution using this chitosan solution;Then gelatin will be contained
Spinning solution and chitosan spinning solution be loaded into successively respectively in 8 adjacent liquid baths of electrostatic spinning machine, and adjacent liquid bath
The composition composition of middle loaded spinning solution is differed, and prepares spinning;
Described electrostatic spinning machine is drum-type electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the roller of drum-type electrostatic spinning machine;
Electrostatic spinning is carried out by drum-type electrostatic spinning machine, using roller of the surface with cloth as receiver;Wherein, spinning
Condition be:
A) delivery rate of spinning solution is 30ml/h;B) environment temperature is 90 DEG C;C) voltage is 200kv;D) spinneret with
The distance between receiver is 100cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 100rpm;Chitosan is spun
The rotating speed being pivoted of the spinneret of silk liquid is 100rpm;F) rotary rpm of roller receiver is 5000rpm;G) receiver
Drying air temperature be 1 DEG C;H) temperature of liquid bath is 35 DEG C;
Described high voltage power supply 6 is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is 50nm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Semi-finished product.The described semi-finished product for alternateing the gelatin-based micro/nano fibrous membrane material for covering the composition that is layering, its adjacent layer
Nanofiber film layer be to be made up of the nanofiber of heterogeneity, the diameter range of nanofiber is 10~30nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based micro/nano fibrous membrane material, which are removed and are soaked in water, carries out crosslinking 1 hour, and temperature when being crosslinked is
30℃;It is washed with deionized, dries after the completion of crosslinking;
(3) semi-finished product of the gelatin-based micro/nano fibrous membrane material obtained after step (2) is dried irradiate 10 under gamma-rays
Hour carries out sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 50nm through needleless electrostatic spinning.
The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 0.013%.
Embodiment 4
As shown in figure 4, structure and the implementation of rotary shaft electrostatic spinning machine for preparing gelatin-based micro/nano fibrous membrane material
The structure of the sea whelk formula electrostatic spinning machine of example 1 is essentially identical, simply changes spinneret, sea whelk spinneret is changed into rotating shaft spinning
Head.
Gelatin-based micro/nano fibrous membrane material is prepared using above-mentioned rotary shaft electrostatic spinning machine.
(1) use molecular weight for 100,000 gelatin, gelatin is dissolved in 10wt% ethanol solution, stir to completely molten
Solution, obtains gelatin solution;Chitosan oligosaccharide is soluble in water, stir to being completely dissolved, obtain chitosan oligosaccharide solution;Then to gelatin solution
Middle addition sodium alginate, continues stirring and obtains the spinning solution containing gelatin to after forming homogeneous (uniform) fluid solution in 5 hours;Wherein contain
The content of gelatin is 80wt% in the solute of the spinning solution of gelatin, and the content of sodium alginate is 20wt%;Chitosan solution it is molten
The content of chitosan is 100wt% in matter, and is used as spinning solution using this chitosan solution;Then by the spinning solution containing gelatin and
Chitosan oligosaccharide spinning solution is loaded into 4 adjacent liquid baths of electrostatic spinning machine successively respectively, and loaded in adjacent liquid bath
The composition composition of spinning solution is differed, and prepares spinning;
Described electrostatic spinning machine is rotary shaft electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the rotating shaft of rotary shaft electrostatic spinning machine;
Electrostatic spinning is carried out by rotary shaft electrostatic spinning machine, using roller of the surface with cloth as receiver;Wherein, spinning
Condition be:
A) delivery rate of spinning solution is 60ml/h;B) environment temperature is 40 DEG C;C) voltage is 70kv;D) spinneret is with connecing
It is 15cm to receive the distance between device;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 30rpm;Chitosan oligosaccharide spinning solution
Spinneret the rotating speed being pivoted be 10rpm;F) rotary rpm of roller receiver is 550rpm;G) drying of receiver
Air temperature is 80 DEG C;H) temperature of liquid bath is 35 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 1cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based micro/nano fibrous membrane material for covering the composition that is layering, its adjacent layer
Nanofiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 50~400nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based micro/nano fibrous membrane material remove and be soaked in containing mass percentage concentration for 25% glutaraldehyde water in enter
Row crosslinking 1 hour, temperature when being crosslinked is 0 DEG C;It is washed with deionized after the completion of crosslinking, until in gelatin-based Nanowire
The remaining glutaraldehyde cross-linking agent tieed up on the semi-finished product of membrane material is washed completely, is dried;
(3) semi-finished product of the gelatin-based micro/nano fibrous membrane material obtained after step (2) is dried irradiate 15 under ultraviolet light
Hour carries out sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 1cm through needleless electrostatic spinning.Press
The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 12.7%.
Embodiment 5
As shown in figure 5, structure and the implementation of gear type electrostatic spinning machine for preparing gelatin-based micro/nano fibrous membrane material
The structure of the sea whelk formula electrostatic spinning machine of example 1 is essentially identical, simply changes spinneret, sea whelk spinneret is changed into gear spinneret
(being made up of multiple gears).
Gelatin-based micro/nano fibrous membrane material is prepared using above-mentioned gear type electrostatic spinning machine.
(1) use molecular weight for 12~160,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin to being completely dissolved
Solution;Hyaluronic acid is dissolved in 1wt% sodium chloride solutions, stirs to being completely dissolved, obtains hyaluronic acid solution;Then to bright
Fibrin ferment, glycerin monostearate are added in sol solution, continues to stir 20 hours and is contained to after forming homogeneous (uniform) fluid solution
The spinning solution of gelatin;The content of gelatin is 83.33wt% wherein in the solute of the spinning solution containing gelatin, and the content of fibrin ferment is
8.33wt%, the content of glycerin monostearate is 8.34wt%;The content of hyaluronic acid is in the solute of hyaluronic acid solution
100wt%, and spinning solution is used as using this hyaluronic acid solution;Then by the spinning solution containing gelatin and hyaluronic acid spinning solution point
Be not loaded into successively in 4 adjacent liquid baths of electrostatic spinning machine, and the spinning solution loaded in adjacent liquid bath into packet
Into differing, prepare spinning;
Described electrostatic spinning machine is gear type electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the gear of gear type electrostatic spinning machine;
Electrostatic spinning is carried out by gear type electrostatic spinning machine, using roller of the surface with cloth as receiver;Wherein, spinning
Condition be:
A) delivery rate of spinning solution is 100ml/h;B) environment temperature is 40 DEG C;C) voltage is 70kv;D) spinneret with
The distance between receiver is 15cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 30rpm;Hyaluronic acid is spun
The rotating speed being pivoted of the spinneret of silk liquid is 30rpm;F) rotary rpm of roller receiver is 0.001rpm;G) receiver
Drying air temperature be 80 DEG C;H) temperature of liquid bath is 40 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 3cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based micro/nano fibrous membrane material for covering the composition that is layering, its adjacent layer
Nanofiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 110~380nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based micro/nano fibrous membrane material remove and be soaked in containing mass percentage concentration for 25% glutaraldehyde water in enter
Row crosslinking 1 hour, temperature when being crosslinked is 15 DEG C;It is washed with deionized after the completion of crosslinking, until gelatin-based Nanowire
The remaining glutaraldehyde cross-linking agent tieed up on the semi-finished product of membrane material is washed completely, is dried;
(3) semi-finished product of the gelatin-based micro/nano fibrous membrane material obtained after step (2) is dried irradiate 20 under ultraviolet light
Hour carries out sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 3cm through needleless electrostatic spinning.Press
The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 15.9%.
Embodiment 6
As shown in figure 1, structure and the implementation of spring electrostatic spinning machine for preparing gelatin-based micro/nano fibrous membrane material
The structure of the sea whelk formula electrostatic spinning machine of example 1 is essentially identical, simply changes spinneret, sea whelk spinneret is changed into spring spinning
Head.
Gelatin-based micro/nano fibrous membrane material is prepared using above-mentioned spring electrostatic spinning machine.
(1) use molecular weight for 16~180,000 gelatin, gelatin is dissolved in the aqueous solution, stir to being completely dissolved, obtain
Gelatin solution;Hyaluronic acid is dissolved in 1wt% sodium chloride solutions, stirs to being completely dissolved, obtains hyaluronic acid solution;Then
Fibrin ferment, glycerin monostearate are added into gelatin solution, continues stirring and is obtained to after forming homogeneous (uniform) fluid solution for 24 hours
Spinning solution containing gelatin;The content of gelatin is 79wt%, the content of fibrin ferment wherein in the solute of the spinning solution containing gelatin
For 10.5wt%, the content of glycerin monostearate is 10.5wt%;The content of hyaluronic acid in the solute of hyaluronic acid solution
For 100wt%, and spinning solution is used as using this hyaluronic acid solution;Then by the spinning solution containing gelatin and hyaluronic acid spinning solution
It is loaded into successively respectively in 6 adjacent liquid baths of electrostatic spinning machine, and the composition of the spinning solution loaded in adjacent liquid bath
Composition is differed, and prepares spinning;
Described electrostatic spinning machine is spring electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the spring of spring electrostatic spinning machine;
Electrostatic spinning is carried out by spring electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 100ml/h;B) environment temperature is 40 DEG C;C) voltage is 70kv;D) spinneret with
The distance between receiver is 15cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 30rpm;Hyaluronic acid is spun
The rotating speed being pivoted of the spinneret of silk liquid is 30rpm;F) rotary rpm of roller receiver is 9rpm;G) receiver is dry
Dry air temperature is 80 DEG C;H) temperature of liquid bath is 45 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 3cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based nano fibrous membrane for covering the composition that is layering, the nanometer of its adjacent layer
Fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 45~300nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based nano fibrous membrane remove and be soaked in containing mass percentage concentration for 25% glutaraldehyde water in handed over
Connection 48 hours, temperature when being crosslinked is 30 DEG C;It is washed with deionized after the completion of crosslinking, until making gelatin based nano-fiber
Remaining glutaraldehyde cross-linking agent on the semi-finished product of film is washed completely, is dried;
(3) semi-finished product of the gelatin-based nano fibrous membrane obtained after step (2) is dried irradiate 0.1 hour under gamma-rays
Sterilization treatment is carried out, thus gelatin-based micro/nano fibrous membrane material is prepared through needleless electrostatic spinning.Carried out according to ninhydrin method
The test of the degree of cross linking, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 50.5%.
Embodiment 7
Carry out preparing gelatin-based micro/nano fibrous membrane material using the sea whelk formula electrostatic spinning machine of embodiment 1.
(1) use molecular weight for 30,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin solution to being completely dissolved;
Hyaluronic acid is dissolved in 1wt% sodium chloride solutions, stirs to being completely dissolved, obtains hyaluronic acid solution;Then it is molten to gelatin
Fibrin ferment, pseudo-ginseng, the third EtOH Stearic fat are added in liquid, continues to stir 30 hours and is contained to after forming homogeneous (uniform) fluid solution
The spinning solution of gelatin;The content of gelatin is 45.45wt% wherein in the solute of the spinning solution containing gelatin, and the content of fibrin ferment is
18.18wt%, the content of pseudo-ginseng is 18.18wt%, and the content of the third EtOH Stearic fat is 18.19wt%;Hyaluronic acid solution
Solute in the content of hyaluronic acid be 100wt%, and spinning solution is used as using this hyaluronic acid solution;Then gelatin will be contained
Spinning solution and hyaluronic acid spinning solution are loaded into 6 adjacent liquid baths of electrostatic spinning machine successively respectively, and adjacent liquid bath
The composition composition of middle loaded spinning solution is differed, and prepares spinning;
Described electrostatic spinning machine is sea whelk formula electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret (being made up of multiple sea whelks) is the sea whelk of sea whelk formula electrostatic spinning machine;
Electrostatic spinning is carried out by sea whelk formula electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 300ml/h;B) environment temperature is 40 DEG C;C) voltage is 150kv;D) spinneret with
The distance between receiver is 15cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 30rpm;Hyaluronic acid is spun
The rotating speed being pivoted of the spinneret of silk liquid is 30rpm;F) rotary rpm of roller receiver is 9rpm;G) receiver is dry
Dry air temperature is 90 DEG C;H) temperature of liquid bath is 30 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 4cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based nano fibrous membrane for covering the composition that is layering, the nanometer of its adjacent layer
Fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 90~450nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
It is 5% butanedial that the semi-finished product for the gelatin-based nano fibrous membrane that nanofiber is constituted, which are removed and are soaked in containing mass percentage concentration,
Water in carry out crosslinking 24 hours, temperature when being crosslinked is 30 DEG C;It is washed with deionized after the completion of crosslinking, until making bright
Remaining butanedial crosslinking agent on the semi-finished product of matrix nano fibrous membrane is washed completely, is dried;
(3) semi-finished product of the gelatin-based nano fibrous membrane obtained after step (2) is dried irradiate 10 hours under ultraviolet light
Sterilization treatment is carried out, thus gelatin-based micro/nano fibrous membrane material is prepared through needleless electrostatic spinning.Carried out according to ninhydrin method
The test of the degree of cross linking, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 16.1%.
Embodiment 8
Carry out preparing gelatin-based micro nanometer fiber membrane material using the spring electrostatic spinning machine of embodiment 6.
(1) use molecular weight for 30,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin solution to being completely dissolved;
Sodium carboxymethylcellulose is soluble in water, stir to being completely dissolved, obtain carboxymethylcellulose sodium solution;Then to gelatin solution
Middle addition fibrin ferment, pseudo-ginseng, the third EtOH Stearic fat, continue stirring and are obtained to after forming homogeneous (uniform) fluid solution containing bright for 30 hours
The spinning solution of glue;The content of gelatin is 72wt% wherein in the solute of the spinning solution containing gelatin, and the content of fibrin ferment is
8wt%, the content of pseudo-ginseng is 12wt%, and the content of the third EtOH Stearic fat is 8wt%;The solute of carboxymethylcellulose sodium solution
The content of middle sodium carboxymethylcellulose is 100wt%, and is used as spinning solution using this carboxymethylcellulose sodium solution;Then it will contain
The spinning solution and sodium carboxymethylcellulose spinning solution of gelatin are loaded into 4 adjacent liquid baths of electrostatic spinning machine successively respectively,
And the composition composition of the spinning solution loaded in adjacent liquid bath is differed, and prepares spinning;
Described electrostatic spinning machine is spring electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the spring of spring electrostatic spinning machine;
Electrostatic spinning is carried out by spring electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 200ml/h;B) environment temperature is 50 DEG C;C) voltage is 180kv;D) spinneret with
The distance between receiver is 13cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 20rpm;Carboxymethyl cellulose
The rotating speed being pivoted of the spinneret of plain sodium spinning solution is 30rpm;F) rotary rpm of roller receiver is 90rpm;G) connect
The drying air temperature for receiving device is 80 DEG C;H) temperature of liquid bath is 40 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains by transversely arranged micro nanometer fiber film layer and longitudinal direction
The micro nanometer fiber film layer of arrangement alternates the gelatin-based micro nanometer fiber membrane material for covering the thickness for the composition that is layering for 2cm
The semi-finished product of material.The described semi-finished product for alternateing the gelatin-based micro nanometer fiber film for covering the composition that is layering, its is adjacent
The micro nanometer fiber film layer of layer is made up of the micro nanometer fiber of heterogeneity, the diameter range of micro nanometer fiber for 800nm~
30μm;
(2) it is made up of what is obtained on the receiver after the completion of step (1) electrostatic spinning alternate micro nanometer fiber in length and breadth
Gelatin-based micro nanometer fiber membrane material semi-finished product remove and be soaked in containing mass percentage concentration be 15% butanedial water
Middle to carry out crosslinking 96 hours, temperature when being crosslinked is 30 DEG C;It is washed with deionized after the completion of crosslinking, until making gelatin-based
Remaining butanedial crosslinking agent on the semi-finished product of micro nanometer fiber membrane material is washed completely, is dried;
(3) semi-finished product of the gelatin-based micro nanometer fiber membrane material obtained after step (2) is dried irradiate under gamma-rays
Carry out sterilization treatment within 10 hours, thus prepare the gelatin-based micro nanometer fiber membrane material that thickness is 2cm through needleless electrostatic spinning
Material.The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 40.7%.
Embodiment 9
Carry out preparing gelatin-based micro/nano fibrous membrane material, and more changing-over using the sea whelk formula electrostatic spinning machine of embodiment 1
Device is received, roller receiver is changed to flat receiver.
Gelatin-based micro/nano fibrous membrane material is prepared using above-mentioned sea whelk formula electrostatic spinning machine.
(1) use molecular weight for 30,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin solution to being completely dissolved;
Agar is soluble in water, stir to being completely dissolved, obtain agar solution;Then fibrin ferment, the root of Dahurain angelica are added into gelatin solution, is gathered
Glyceride fatty esters, continue stirring and obtain the spinning solution containing gelatin to after forming homogeneous (uniform) fluid solution in 20 hours;Wherein contain
Have gelatin spinning solution solute in the content of gelatin be 72wt%, the content of fibrin ferment is 8wt%, and the content of the root of Dahurain angelica is
12wt%, the content of polyglycerol ester fatty acid ester is 8wt%;The content of agar is 100wt% in the solute of agar solution, and with
This agar solution is used as spinning solution;Then the spinning solution containing gelatin and agar spinning solution are loaded into electrostatic spinning successively respectively
In 4 adjacent liquid baths of machine, and the composition composition of the spinning solution loaded in adjacent liquid bath is differed, and prepares spinning;
Described electrostatic spinning machine is sea whelk formula electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret (being made up of multiple sea whelks) is the sea whelk of sea whelk formula electrostatic spinning machine;
Electrostatic spinning is carried out by sea whelk formula electrostatic spinning machine, using flat board of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 100ml/h;B) environment temperature is 40 DEG C;C) voltage is 70kv;D) spinneret with
The distance between receiver is 30cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 50rpm;Agar spinning solution
Spinneret the rotating speed being pivoted be 80rpm;F) linear velocity of flat receiver is 50m/min;G) drying of receiver
Air temperature is 80 DEG C;H) temperature of liquid bath is 3 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is 4.9cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Semi-finished product.It is described alternate covering be layering composition gelatin-based nano fibrous membrane semi-finished product, its adjacent layer receives
Rice fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 65~340nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
It is 7% butanedial that the semi-finished product for the gelatin-based nano fibrous membrane that nanofiber is constituted, which are removed and are soaked in containing mass percentage concentration,
Water in carry out crosslinking 144 hours, temperature during crosslinking is 30 DEG C;It is washed with deionized after the completion of crosslinking, until making gelatin
Remaining butanedial crosslinking agent on the semi-finished product of based nano-fiber film is washed completely, is dried;
(3) semi-finished product of the gelatin-based nano fibrous membrane obtained after step (2) is dried irradiate 5 hours under ultraviolet light
Row sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 4.9cm through needleless electrostatic spinning.According to indenes
Triketone method carries out the test of the degree of cross linking, and the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 27.2%.
Embodiment 10
Carry out preparing gelatin-based micro/nano fibrous membrane material using the sea whelk formula electrostatic spinning machine of embodiment 1.
(1) use molecular weight for 30,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin solution to being completely dissolved;
Fibroin albumen is soluble in water, stir to being completely dissolved, obtain silk fibroin protein solution, blood coagulation is then added into gelatin solution
Enzyme, the root of Dahurain angelica, polyglycerol ester fatty acid ester, continue to obtain the spinning containing gelatin after stirring forms homogeneous (uniform) fluid solution in 10 hours
Liquid;The content of gelatin is 70wt% wherein in the solute of the spinning solution containing gelatin, and the content of fibrin ferment is 10wt%, the root of Dahurain angelica
Content is 10wt%, and the content of polyglycerol ester fatty acid ester is 10wt%;Fibroin albumen contains in the solute of silk fibroin protein solution
Measure as 100wt%, and spinning solution is used as using this silk fibroin protein solution;Then by the spinning solution containing gelatin and fibroin albumen spinning
Liquid is loaded into 4 adjacent liquid baths of electrostatic spinning machine successively respectively, and the spinning solution loaded in adjacent liquid bath into
It is grouped into and differs, prepares spinning;
Described electrostatic spinning machine is sea whelk formula electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret (being made up of multiple sea whelks) is the sea whelk of sea whelk formula electrostatic spinning machine;
Electrostatic spinning is carried out by sea whelk formula electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 10ml/h;B) environment temperature is 40 DEG C;C) voltage is 70kv;D) spinneret is with connecing
It is 13cm to receive the distance between device;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 20rpm;Fibroin albumen spinning
The rotating speed being pivoted of the spinneret of liquid is 30rpm;F) rotary rpm of roller receiver is 250rpm;G) receiver is dry
Dry air temperature is 80 DEG C;H) temperature of liquid bath is 55 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is 0.1cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Semi-finished product.It is described alternate covering be layering composition gelatin-based nano fibrous membrane semi-finished product, its adjacent layer receives
Rice fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 72~334nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based micro/nano fibrous membrane material are removed and are soaked in concentration to carry out in 50mmol/L carbodiimide ethanol solutions
Crosslinking 168 hours, temperature during crosslinking is 30 DEG C;It is washed with deionized after the completion of crosslinking, until making gelatin based nano-fiber
Remaining carbodiimide ethanol crosslinking agent on the semi-finished product of membrane material is washed completely, is dried;
(3) it is small that the semi-finished product of the gelatin-based micro/nano fibrous membrane material obtained after step (2) is dried irradiate 9 under ultraviolet light
Shi Jinhang sterilization treatments, thus prepare the gelatin-based micro/nano fibrous membrane material that thickness is 0.1cm through needleless electrostatic spinning.Press
The test of the degree of cross linking is carried out according to ninhydrin method, the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 18.5%.
Embodiment 11
Carry out preparing gelatin-based micro/nano fibrous membrane material using the screw electrostatic spinning machine of embodiment 2.
(1) use molecular weight for 110,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin solution to being completely dissolved;
Fibroin albumen is soluble in water, stir to being completely dissolved, obtain silk fibroin protein solution, blood coagulation is then added into gelatin solution
Enzyme, the root of Dahurain angelica, polyglycerol ester fatty acid ester, continue to obtain the spinning containing gelatin after stirring forms homogeneous (uniform) fluid solution in 10 hours
Liquid;The content of gelatin is 60wt% wherein in the solute of the spinning solution containing gelatin, and the content of fibrin ferment is 17.5wt%, the root of Dahurain angelica
Content be 17.5wt%, the content of polyglycerol ester fatty acid ester is 5wt%;Fibroin albumen in the solute of silk fibroin protein solution
Content is 100wt%, and is used as spinning solution using this silk fibroin protein solution;Then the spinning solution containing gelatin and fibroin albumen are spun
Silk liquid is loaded into 4 adjacent liquid baths of electrostatic spinning machine successively respectively, and the spinning solution loaded in adjacent liquid bath
Composition composition is differed, and prepares spinning;
Described electrostatic spinning machine is screw electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the screw rod of screw electrostatic spinning machine;
Electrostatic spinning is carried out by screw electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 100ml/h;B) environment temperature is 40 DEG C;C) voltage is 140kv;D) spinneret with
The distance between receiver is 15cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 20rpm;Fibroin albumen is spun
The rotating speed being pivoted of the liquid spinneret of silk is 20rpm;F) rotary rpm of roller receiver is 650rpm;G) receiver
It is 80 DEG C to dry air temperature;H) temperature of liquid bath is 45 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 3cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based nano fibrous membrane for covering the composition that is layering, the nanometer of its adjacent layer
Fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 40~220nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based nano fibrous membrane are removed and are soaked in concentration to be crosslinked in 100mmol/L carbodiimide ethanol solutions
168 hours, temperature during crosslinking was 30 DEG C;It is washed with deionized after the completion of crosslinking, until making gelatin-based nano fibrous membrane
Remaining carbodiimide cross-linking agent on semi-finished product is washed completely, is dried;
(3) semi-finished product of the gelatin-based nano fibrous membrane obtained after step (2) is dried irradiate 6 hours under ultraviolet light
Row sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 3cm through needleless electrostatic spinning.According to indenes three
Ketone method carries out the test of the degree of cross linking, and the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 29.3%.
Embodiment 12
Carry out preparing gelatin-based micro/nano fibrous membrane material using the sea whelk formula electrostatic spinning machine of embodiment 1.
(1) use molecular weight for 8~100,000 gelatin, gelatin is soluble in water, and stirring obtains gelatin molten to being completely dissolved
Liquid;Pla-pcl is dissolved in dichloromethane solution, stirs to being completely dissolved, obtains pla-pcl solution, it is then molten to gelatin
Hydroxyapatite, Norfloxacin, polyglycerol ester fatty acid ester are added in liquid, continues to stir after 20 hours formation homogeneous (uniform) fluid solution
Obtain the spinning solution containing gelatin;The content of gelatin is 50wt%, hydroxy-apatite wherein in the solute of the spinning solution containing gelatin
The content of stone is 25wt%, and the content of Norfloxacin is 12.5wt%, and the content of polyglycerol ester fatty acid ester is 12.5wt%;It is poly-
The content of pla-pcl is 100wt% in the solute of caprolactone solution, and is used as spinning solution using this pla-pcl solution;Then will
Spinning solution containing gelatin and pla-pcl spinning solution are loaded into 6 adjacent liquid baths of electrostatic spinning machine successively respectively, and
The composition composition of the spinning solution loaded in adjacent liquid bath is differed, and prepares spinning;
Described electrostatic spinning machine is sea whelk formula electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret (being made up of multiple sea whelks) is the sea whelk of sea whelk formula electrostatic spinning machine;
Electrostatic spinning is carried out by sea whelk formula electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 300ml/h;B) environment temperature is 50 DEG C;C) voltage is 70kv;D) spinneret with
The distance between receiver is 25cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 20rpm;Pla-pcl is spun
The rotating speed being pivoted of the spinneret of silk liquid is 15rpm;F) rotary rpm of roller receiver is 300rpm;G) receiver
It is 90 DEG C to dry air temperature;H) temperature of liquid bath is 45 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 3cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based nano fibrous membrane for covering the composition that is layering, the nanometer of its adjacent layer
Fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 150~600nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of matrix nano fibrous membrane are removed and are soaked in concentration to carry out crosslinking 72 in 50mmol/L carbodiimide ethanol solutions
Hour, temperature during crosslinking is 30 DEG C;Be washed with deionized after the completion of crosslinking, until make the half of gelatin-based nano fibrous membrane into
Remaining carbodiimide cross-linking agent on product is washed completely, is dried;
(3) semi-finished product of the matrix nano fibrous membrane obtained after step (2) is dried irradiate 12 hours under ultraviolet light
Row sterilization treatment, thus prepares the gelatin-based micro/nano fibrous membrane material that thickness is 3cm through needleless electrostatic spinning.According to indenes three
Ketone method carries out the test of the degree of cross linking, and the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 23.7%.
Embodiment 13
Carry out preparing gelatin-based micro/nano fibrous membrane material using the spring electrostatic spinning machine of embodiment 6.
(1) use molecular weight for 20,000 gelatin, gelatin is dissolved in the acetum that mass concentration is 1%, stirred to complete
Fully dissolved, obtains gelatin solution;Collagen is soluble in water, stir to being completely dissolved, obtain collagen solution, Ran Houxiang
Hydroxyapatite, Norfloxacin, polyglycerol ester fatty acid ester are added in gelatin solution, continues to stir 24 hours formation homogeneous (uniform) fluids
The spinning solution containing gelatin is obtained after solution;The content of gelatin is 50wt%, hydroxyl wherein in the solute of the spinning solution containing gelatin
The content of base apatite is 25wt%, and the content of Norfloxacin is 12.5wt%, and the content of polyglycerol ester fatty acid ester is
12.5wt%;The content of collagen is 100wt% in the solute of collagen solution, and is used as spinning using this collagen solution
Silk liquid;Then by the spinning solution containing gelatin and collagen spinning solution be loaded into successively respectively 4 of electrostatic spinning machine it is adjacent
Liquid bath in, and the composition composition of the spinning solution loaded in adjacent liquid bath differs, and prepares spinning;
Described electrostatic spinning machine is spring electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the spring of spring electrostatic spinning machine;
Electrostatic spinning is carried out by spring electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 200ml/h;B) environment temperature is 50 DEG C;C) voltage is 150kv;D) spinneret with
The distance between receiver is 25cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 30rpm;Collagen is spun
The rotating speed being pivoted of the spinneret of silk liquid is 15rpm;F) rotary rpm of roller receiver is 300rpm;G) receiver
It is 90 DEG C to dry air temperature;H) temperature of liquid bath is 45 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 3cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based nano fibrous membrane for covering the composition that is layering, the nanometer of its adjacent layer
Fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 210~570nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based nano fibrous membrane remove the steaming for being placed in and being volatilized containing mass percentage concentration by the 10% Geniposide aqueous solution
Crosslinking 24 hours is carried out in vapour;Temperature when being crosslinked is 30 DEG C;It is washed with deionized after the completion of crosslinking, until making gelatin
Remaining Geniposide crosslinking agent on the semi-finished product of based nano-fiber film is washed completely, is dried;
(3) semi-finished product of the gelatin-based nano fibrous membrane obtained after step (2) is dried irradiate 15 hours under ultraviolet light
Sterilization treatment is carried out, thus the gelatin-based micro/nano fibrous membrane material that thickness is 3cm is prepared through needleless electrostatic spinning.According to indenes
Triketone method carries out the test of the degree of cross linking, and the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 18.9%.
Embodiment 14
Carry out preparing gelatin-based micro/nano fibrous membrane material using the screw electrostatic spinning machine of embodiment 2.
(1) use molecular weight for 4~70,000 gelatin, gelatin be dissolved in 3% formic acid solution, stirring to being completely dissolved,
Obtain gelatin solution;Pla-pcl is dissolved in tetrahydrofuran solution, stirs to being completely dissolved, obtains pla-pcl solution;So
Hydroxyapatite, Norfloxacin, polyglycerol ester fatty acid ester are added in backward gelatin solution, continues stirring and forms within 24 hours uniform
The spinning solution containing gelatin is obtained after fluid solution;Wherein the content of gelatin is in the solute of the spinning solution containing gelatin
50wt%, the content of hydroxyapatite is 37.5wt%, and the content of Norfloxacin is 7.5wt%, polyglycerol ester fatty acid ester
Content is 5wt%;The content of pla-pcl is 100wt% in the solute of pla-pcl solution, and is made with this pla-pcl solution
For spinning solution;Then spinning solution containing gelatin and pla-pcl spinning solution are loaded into 4 of electrostatic spinning machine successively respectively
In adjacent liquid bath, and the composition composition of the spinning solution loaded in adjacent liquid bath is differed, and prepares spinning;
Described electrostatic spinning machine is screw electrostatic spinning machine;The spinning of electrostatic spinning machine in described adjacent liquid bath
Silk head is the spinneret of one horizontal direction of placement in the spinneret of one longitudinal direction of placement in a liquid bath, a liquid bath
Over-over mode is placed;Described spinneret is the screw rod of screw electrostatic spinning machine;
Electrostatic spinning is carried out by screw electrostatic spinning machine, using roller of the surface with aluminium foil as receiver;Wherein, spin
Silk condition be:
A) delivery rate of spinning solution is 300ml/h;B) environment temperature is 50 DEG C;C) voltage is 150kv;D) spinneret with
The distance between receiver is 25cm;E) rotating speed being pivoted of the spinneret of gelatin spinning solution is 30rpm;Pla-pcl is spun
The rotating speed being pivoted of the spinneret of silk liquid is 15rpm;F) rotary rpm of roller receiver is 500rpm;G) receiver
It is 90 DEG C to dry air temperature;H) temperature of liquid bath is 45 DEG C;
Described high voltage power supply is opened, electrostatic spinning is carried out, obtains being arranged with longitudinal direction by transversely arranged nanofiber film layer
It is the half of 3cm gelatin-based micro/nano fibrous membrane material that the nanofiber film layer of row, which alternates and covers the thickness for the composition that is layering,
Finished product.The described semi-finished product for alternateing the gelatin-based nano fibrous membrane for covering the composition that is layering, the nanometer of its adjacent layer
Fiber film layer is made up of the nanofiber of heterogeneity, and the diameter range of nanofiber is 130~630nm;
(2) by being made up of alternate nanofiber in length and breadth of being obtained on the receiver after the completion of step (1) electrostatic spinning
The semi-finished product of gelatin-based nano fibrous membrane are removed and are soaked in concentration to be crosslinked in 50mmol/L carbodiimide ethanol solutions
48 hours, temperature during crosslinking was 30 DEG C;It is washed with deionized after the completion of crosslinking, until making the half of gelatin-based nano fibrous membrane
Remaining carbodiimide cross-linking agent on finished product is washed completely, is dried;
(3) semi-finished product of the gelatin-based nano fibrous membrane obtained after step (2) is dried irradiate 20 hours under ultraviolet light
Sterilization treatment is carried out, thus the gelatin-based micro/nano fibrous membrane material that thickness is 3cm is prepared through needleless electrostatic spinning.According to indenes
Triketone method carries out the test of the degree of cross linking, and the degree of cross linking of gelatin-based micro/nano fibrous membrane material is 14.6%.