CN107354586A - A kind of γ polyglutamic acids polyacrylonitrile composite nanofiber membrane and preparation method thereof - Google Patents
A kind of γ polyglutamic acids polyacrylonitrile composite nanofiber membrane and preparation method thereof Download PDFInfo
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- CN107354586A CN107354586A CN201710511395.5A CN201710511395A CN107354586A CN 107354586 A CN107354586 A CN 107354586A CN 201710511395 A CN201710511395 A CN 201710511395A CN 107354586 A CN107354586 A CN 107354586A
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- polyacrylonitrile
- polyglutamic acid
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- nanofiber membrane
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 58
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 229920002643 polyglutamic acid Polymers 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 31
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 37
- 238000009987 spinning Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- 238000004113 cell culture Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000002062 proliferating effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-GSVOUGTGSA-N D-glutamic acid Chemical compound OC(=O)[C@H](N)CCC(O)=O WHUUTDBJXJRKMK-GSVOUGTGSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of γ polyglutamic acids polyacrylonitrile composite nanofiber membrane and preparation method thereof, by γ polyglutamic acids and polyacrylonitrile, (1: 10 5: 6) are dissolved in N, N dimethylformamide and trifluoroacetic acid complex solvent that volume ratio is 21: 1 according to a certain percentage, the homogeneous solution of finite concentration (11% 18%) is configured to, composite nano-fiber membrane is prepared into by electrostatic spinning technique.The nano fibrous membrane that the present invention prepares gained has network structure, γ polyglutamic acids have good water-retaining property, biocompatibility, polyacrylonitrile has good chemical stability and mechanical performance, and product can be widely used in the fields such as raw body tissue cultures, medical accessory.
Description
Technical field
The invention belongs to technical field of biological material, it is related to the preparation method of gamma-polyglutamic acid nano fibrous membrane, more particularly to one
Kind prepares the preparation method of gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane by electrostatic spinning process.
Technical background
It is a kind of relatively easy easy technology by electrospun nanofibers film, the nanofiber membrane material of preparation
Material has that specific surface area is big, the advantages such as micro-porosity is high, connectivity is good, be separated by filtration, organizational project, medical material, biology
There is good application prospect in the fields such as cell culture.
Gamma-polyglutamic acid is a kind of polymeric anion type polypeptide type polymer, mainly by the different paddy of two types
Propylhomoserin:D-Glu and Pidolidone are formed in a manner of polymerizeing, more at present to be prepared with microbe fermentation method.Gamma-polyglutamic acid
With water-soluble fabulous, absorption property is strong, can natural degradation, it is nontoxic, the characteristic such as edible, it is had in every field
It is widely applied prospect.
Polyacrylonitrile is through Raolical polymerizable system, for white or the powder thing of yellowish by monomers acrylonitrile
Matter, there is good chemicals-resistant stability, light resistance and fungus resistance, and hydrolytic resistance and inoxidizability very well, extensively
The preparation for being applied to fiber-like and membrane-based article.
In existing technology, gamma-polyglutamic acid is because with substantial amounts of hydrophilic radical, intermolecular degree of entanglement is higher, adopts
Nanofiber can not be prepared with electrostatic spinning technique.After the nanofiber film preparation of some addition gamma-polyglutamic acids, from the steady of film
Qualitative angle is set out, and is both needed to, using post processing, such as hydroformylation, influence be generated on the performance of gamma-polyglutamic acid.The present invention passes through
Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane prepared by electrostatic spinning process need not post-process can and keep steady
Fixed state and performance;On the other hand, gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane that prepared by the present invention is non-toxic,
Also there is very prominent performance in terms of cell culture.
The content of the invention
It is an object of the invention to provide a kind of gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane and preparation method thereof.
The technical issues that need to address are the present invention to achieve the above object, and searching is suitable for gamma-polyglutamic acid, polypropylene
Solvent and gamma-polyglutamic acid, the material rate of polyacrylonitrile prepared by nitrile electrostatic spinning liquid.
The present invention is that technical scheme is used by solving above-mentioned technical problem:A kind of gamma-polyglutamic acid-polyacrylonitrile is multiple
Close nano fibrous membrane and preparation method thereof, it is characterised in that comprise the following steps:
Using N, N --- it is molten to configure the compounding that volume ratio is 21: 1 as solvent for dimethylformamide, trifluoroacetic acid
Agent, it is standby;
The use of gamma-polyglutamic acid and polyacrylonitrile is solute, it is standby
It is 11%-18% according to mass percent concentration, calculates respectively, weighs above-mentioned complex solvent and solute, wherein molten
Gamma-polyglutamic acid and polyacrylonitrile in mass ratio 1: 10-5: 6, are weighed respectively in matter;
The gamma-polyglutamic acid weighed is added in above-mentioned complex solvent, is sufficiently stirred and uniform solution A is made.
The polyacrylonitrile powder weighed is added in solution A, is sufficiently stirred, uniform mixed solution B is made.
The mixed solution B of gained is placed in supersonic generator and carries out deaeration, spinning solution is made;
Using electrospinning device, gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is prepared.
The technical effect directly brought by the technical proposal is that preparation technology flow is short, process controllability is high, product shape
State, stable performance, it is not required to post-process, can preserves for a long time under normal conditions.
Prepared gamma-polyglutamic acid-polyacrylonitrile nanofiber film can be widely used in raw body cell, tissue training
The fields such as foster, medical accessory.
In above-mentioned technical proposal, one of key problem in technology point is N, N in solvent --- dimethylformamide, trifluoroacetic acid are answered
With ratio:
Gamma-polyglutamic acid is dissolved in trifluoroacetic acid, is insoluble in N, N --- dimethylformamide.The ratio of trifluoroacetic acid is low then
The dissolving of gamma-polyglutamic acid can be influenceed, it is difficult to form the spinning solution of stable and uniform;The ratio of trifluoroacetic acid is high, electrostatic spinning into
This increase, equipment and requirement of shelter are improved.
In above-mentioned technical proposal, another key problem in technology point is the configuration mode of spinning solution:
When preparing gamma-polyglutamic acid-polyacrylonitrile electrostatic spinning liquid, γ-polyglutamic is added first in complex solvent
Acid, continue stirring until dissolving and form stable homogeneous phase solution, then add polyacrylonitrile powder into the solution again, until stirring molten
Solution is into stablizing homogeneous mixed solution.By such priority charging sequence, it can effectively prevent gamma-polyglutamic acid from occurring not
Molten phenomenon.
In above-mentioned technical proposal, control gamma-polyglutamic acid and polyacrylonitrile mass ratio to be up to 5: 6 main purpose and be
Prevent the drop for excessively tangling the beading phenomenon and spinning property that cause composite nano-fiber membrane between gamma-polyglutamic acid molecule
It is low.
Brief description of the drawings
Fig. 1 blank samples cell culture experiments (first day)
Fig. 2 blank samples cell culture experiments (the 3rd day)
Fig. 3 gamma-polyglutamic acids-polyacrylonitrile composite nanofiber membrane sample cell culture experiment (first day)
Fig. 4 gamma-polyglutamic acids-polyacrylonitrile composite nanofiber membrane sample cell culture experiment (the 3rd day)
Embodiment
With reference to embodiment, the present invention is described in detail.
Explanation:
In 1 following examples, gamma-polyglutamic acid molecular weight is 700,000, and the molecular weight of polyacrylonitrile is 150,000.
2 gamma-polyglutamic acids-polyacrylonitrile composite nanofiber membrane tension failure method for testing strength is as follows:
Gamma-polyglutamic acid-polyacrylonitrile nanofiber membrane sample is cut, by sample holder on material electronicses strength machine,
Clamp distance is 15mm, draw speed 100mm/min, and it is strong to test its tension failure with reference to international standard ISO 9073-3-1989
Power.
3 gamma-polyglutamic acids-polyacrylonitrile nanofiber film is used for mouse cell cell culture, is detected by mtt assay thin
Born of the same parents' proliferative conditions, light absorption value OD values represent cell proliferative conditions.
Embodiment 1
(1) using N, N --- dimethylformamide, trifluoroacetic acid combination solution are as solvent, wherein volume ratio 21: 1 is configured,
Configure solvent 30ml.
(2) it is 11% according to mass percent concentration, calculates, weighs solute, gamma-polyglutamic acid and poly- third wherein in solute
Alkene nitrile is 1: 10 in mass ratio;
(3) gamma-polyglutamic acid weighed is added in above-mentioned complex solvent, is sufficiently stirred and uniform solution is made
A.The polyacrylonitrile powder weighed is added in solution A, is sufficiently stirred, uniform mixed solution B is made.By the mixed of gained
Close solution B and be placed in progress deaeration in supersonic generator, spinning solution is made;
(4) electrostatic spinning is utilized, is 21KV in spinning voltage, the distance of shower nozzle to receiver is 15cm, and spinning solution enters
Under the conditions of being 0.8ml/h to flow velocity, gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is prepared.
(5) test of product performance and testing result:Gamma-polyglutamic acid-polyacrylonitrile nanofiber film stretching ultimate strength
For 1053.00cN/mm;Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is used for mouse cell cell culture, blank
First day OD value of cell culture experiments is 14000, and the 3rd day is 18500;Gamma-polyglutamic acid-polyacrylonitrile composite nano fiber
First day OD value of Membrance cuiture cell sample reaches 17000, reaches 21000 within the 3rd day.
Embodiment 2
(1) using N, N --- dimethylformamide, trifluoroacetic acid combination solution are as solvent, wherein volume ratio 21: 1 is configured,
Configure solvent 30ml.
(2) it is 12% according to mass percent concentration, calculates, weighs solute, gamma-polyglutamic acid and poly- third wherein in solute
Alkene nitrile mass ratio is 2: 9;
(3) gamma-polyglutamic acid weighed is added in above-mentioned complex solvent, is sufficiently stirred and uniform solution is made
A.The polyacrylonitrile powder weighed is added in solution A, is sufficiently stirred, uniform mixed solution B is made.By the mixed of gained
Close solution B and be placed in progress deaeration in supersonic generator, spinning solution is made;
(4) electrostatic spinning is utilized, is 22KV in spinning voltage, the distance of shower nozzle to receiver is 20cm, and spinning solution enters
Under the conditions of being 0.2ml/h to flow velocity, gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is prepared.
(5) test of product performance and testing result:Gamma-polyglutamic acid-polyacrylonitrile nanofiber film stretching ultimate strength
For 1022.5cN/mm;Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is used for mouse cell cell culture, blank is thin
First day OD value of born of the same parents' culture experiment is 14000, and the 3rd day is 18500;Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane
Culture first day OD value of cell sample reaches 18200, reaches 22300 within the 3rd day.
Embodiment 3
(1) using N, N --- dimethylformamide, trifluoroacetic acid combination solution are as solvent, wherein volume ratio 21: 1 is configured,
Configure solvent 30ml.
(2) it is 13% according to mass percent concentration, calculates, weighs solute, gamma-polyglutamic acid and poly- third wherein in solute
Alkene nitrile mass ratio is 3: 8;
(3) gamma-polyglutamic acid weighed is added in above-mentioned complex solvent, is sufficiently stirred and uniform solution is made
A.The polyacrylonitrile powder weighed is added in solution A, is sufficiently stirred, uniform mixed solution B is made.By the mixed of gained
Close solution B and be placed in progress deaeration in supersonic generator, spinning solution is made;
(4) electrostatic spinning is utilized, is 24KV in spinning voltage, the distance of shower nozzle to receiver is 20cm, and spinning solution enters
Under the conditions of being 0.3ml/h to flow velocity, gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is prepared.
(5) test of product performance and testing result:Gamma-polyglutamic acid-polyacrylonitrile nanofiber film stretching ultimate strength
For 1008.18cN/mm;Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is used for mouse cell cell culture, blank
First day OD value of cell culture experiments is 14000, and the 3rd day is 18500;Gamma-polyglutamic acid-polyacrylonitrile composite nano fiber
First day OD value of Membrance cuiture cell sample reaches 18900, reaches 24000 within the 3rd day.
Embodiment 4
(1) using N, N --- dimethylformamide, trifluoroacetic acid combination solution are as solvent, wherein volume ratio 17: 1 is configured,
Configure solvent 30ml.
(2) it is 11% according to mass percent concentration, calculates, weighs solute, gamma-polyglutamic acid and poly- third wherein in solute
Alkene nitrile mass ratio is 4: 7;
(3) gamma-polyglutamic acid weighed is added in above-mentioned complex solvent, is sufficiently stirred and uniform solution is made
A.The polyacrylonitrile powder weighed is added in solution A, is sufficiently stirred, uniform mixed solution B is made.By the mixed of gained
Close solution B and be placed in progress deaeration in supersonic generator, spinning solution is made;
(4) electrostatic spinning is utilized, is 22KV in spinning voltage, the distance of shower nozzle to receiver is 15cm, and spinning solution enters
Under the conditions of being 0.2ml/h to flow velocity, gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is prepared.
(5) test of product performance and testing result:Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane tension failure
Strength is 1012.3cN/mm;Gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane is used for mouse cell cell culture, it is empty
First day OD value of leucocyte culture experiment is 14000, and the 3rd day is 18500;Gamma-polyglutamic acid-polyacrylonitrile nanofiber film
Culture first day OD value of cell sample reaches 17800, reaches 20900 within the 3rd day.
Claims (5)
1. a kind of gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane and preparation method thereof, it is by N, N --- dimethyl methyl
As solvent, gamma-polyglutamic acid and polyacrylonitrile are solute, configure spinning solution, pass through electrospinning device for acid amides, trifluoroacetic acid
Prepare film forming.Characterized in that, raw material used include:Gamma-polyglutamic acid, polyacrylonitrile, N, N --- dimethyl formyl
Amine, trifluoroacetic acid.
2. a kind of gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane according to claim 1 and preparation method thereof,
Characterized in that, the molecular weight of raw materials used gamma-polyglutamic acid is 700,000, the molecular weight of polyacrylonitrile is 150,000.
3. a kind of gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane according to claim 1 and preparation method thereof,
Characterized in that, described solvent is N, N --- dimethylformamide, trifluoroacetic acid.
A kind of a kind of 4. gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane and its preparation as described in claims 1 to 3
Method, it is characterised in that comprise the following steps:
(1) N, N are used --- dimethylformamide, trifluoroacetic acid use gamma-polyglutamic acid and polyacrylonitrile as complex solvent
For solute, according to certain mass than calculating, weighing above-mentioned complex solvent and solute respectively.
(2) gamma-polyglutamic acid weighed is added in above-mentioned complex solvent, is sufficiently stirred and uniform solution A is made;So
Afterwards, the polyacrylonitrile powder weighed is added in solution A, be sufficiently stirred, uniform mixed solution B is made.
(3) the mixed solution B of gained is placed in supersonic generator and carries out deaeration, spinning solution is made;
(4) electrospinning device is utilized, prepares gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane.
5. a kind of gamma-polyglutamic acid-polyacrylonitrile composite nanofiber membrane according to claim 4 and preparation method thereof
Preparation method, it is characterised in that:
In the step 1, N, N --- dimethylformamide, trifluoroacetic acid compounding volume ratio are 21: 1;
In the step 1, gamma-polyglutamic acid, polyacrylonitrile compounding mass ratio are 1: 10-5: 6;
In the step 1, solute and solvent quality ratio are 11%-18%;
In the step 4, for the spinning voltage that electrostatic spinning uses for 15-25KV, the distance of shower nozzle to receiver is 10-20cm,
Spinning solution feeding flow velocity is 0.1-1.0ml/h.
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CN111979589A (en) * | 2020-07-13 | 2020-11-24 | 安徽宜民服饰股份有限公司 | Nanofiber modification process with good moisture absorption performance |
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CN1460534A (en) * | 2003-05-28 | 2003-12-10 | 东南大学 | Nano fibre protective filtering material and its preparation method |
CN101798756A (en) * | 2010-01-06 | 2010-08-11 | 东华大学 | Method for preparing biomedical material of static self-assembly modified nano fiber |
CN104711771A (en) * | 2015-03-27 | 2015-06-17 | 东华大学 | Method for preparing nanofiber membrane through electrostatic spinning |
CN104742369A (en) * | 2015-03-16 | 2015-07-01 | 东莞劲胜精密组件股份有限公司 | 3D printing device and method |
CN104762753A (en) * | 2014-12-26 | 2015-07-08 | 天津北洋百川生物技术有限公司 | Preparation method of gamma-polyglutamic pullulan nanometer fiber film of load drug |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1460534A (en) * | 2003-05-28 | 2003-12-10 | 东南大学 | Nano fibre protective filtering material and its preparation method |
CN101798756A (en) * | 2010-01-06 | 2010-08-11 | 东华大学 | Method for preparing biomedical material of static self-assembly modified nano fiber |
CN104762753A (en) * | 2014-12-26 | 2015-07-08 | 天津北洋百川生物技术有限公司 | Preparation method of gamma-polyglutamic pullulan nanometer fiber film of load drug |
CN104742369A (en) * | 2015-03-16 | 2015-07-01 | 东莞劲胜精密组件股份有限公司 | 3D printing device and method |
CN104711771A (en) * | 2015-03-27 | 2015-06-17 | 东华大学 | Method for preparing nanofiber membrane through electrostatic spinning |
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CN111979589A (en) * | 2020-07-13 | 2020-11-24 | 安徽宜民服饰股份有限公司 | Nanofiber modification process with good moisture absorption performance |
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