CN109267240A - A kind of medical dressing chitosan/calcium alginate needleless electrostatic spinning nano fiber film and preparation method thereof - Google Patents

A kind of medical dressing chitosan/calcium alginate needleless electrostatic spinning nano fiber film and preparation method thereof Download PDF

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CN109267240A
CN109267240A CN201811385922.3A CN201811385922A CN109267240A CN 109267240 A CN109267240 A CN 109267240A CN 201811385922 A CN201811385922 A CN 201811385922A CN 109267240 A CN109267240 A CN 109267240A
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chitosan
sodium alginate
electrostatic spinning
nano fiber
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CN109267240B (en
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王迎
雷红娜
丁照轩
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Dalian Polytechnic University
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Dalian Polytechnic University
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

Abstract

The present invention relates to a kind of medical dressing chitosan/calcium alginate needleless electrostatic spinning nano fiber films and preparation method thereof, belong to native biopolymer Material Field.By chitosan and PEO (or PVP) solution, sodium alginate soln and PEO (or PVP) solution are respectively placed in the two sides of electrostatic spinning solution box, converge two kinds of solution at spinning head, and during the volatilization of Static Spinning solvent, make sodium alginate, chitosan carries out polyelectrolyte self-crosslinking, obtain a kind of polyelectrolyte electrostatic spinning nano fiber composite membrane of self-crosslinking chitosan/sodium alginate composition, and nano composite membrane is crosslinked using chlorination calcium cross-linked method, it exchanges sodium alginate with divalent calcium ions and generates calcium alginate, acquisition main component is Ah-ACMS composite Nano fibre film.The present invention improves the mechanical property and service performance of material, gives full play to the biocompatibility of chitosan, calcium alginate by electrostatic force and calcium chloride crosslinking synergism.

Description

A kind of medical dressing chitosan/calcium alginate needleless electrostatic spinning nano fiber film and Preparation method
Technical field
The invention belongs to native biopolymer field of material technology, are related to a kind of calcium alginate/chitosan nano meter level doctor With dressing and preparation method thereof.
Background technique
Nanofiber is since it is with very high volume-surface ratio, in organizational project, drug release, medical dressing etc. Field utility value with higher.Electrostatic spinning technique is to prepare the simple and effective method of nanofiber.Dressing absorbs wound Face diffusate sticks together with the surface of a wound simultaneously, and cambium is damaged when causing to remove, brings great pain to patient.And it receives Medical dressing made of rice tunica fibrosa is conducive to the evaporation of wound fluid, is conducive to oxygen transmission, is also beneficial to wound tissue Growth and regeneration in recent years, nano fiber non-woven fabric has been used for medical dressing increasingly so as to accelerate the healing of wound Extensively.
Chitosan is chitin through deacetylation treated product, is natural alkaline polysaccharide present in nature, it It is a kind of environmentally friendly natural polymer.Chitosan has many advantages, such as nontoxic, biocompatibility, biodegradability, Also there are many excellent physiological performances such as cancer resistance, antibiotic property, hemostatic, enhancing human immunological competence, be widely used in group Weaver's journey, drug carrier material and wound dressing etc..Sodium alginate is a kind of natural polymer being present in brown alga Material, it is the linear polymeric for randomly replacing bonded formation by guluronic acid (G sections) and mannuronic acid (M sections).Seaweed Sour sodium is used for food, medicine, daily-use chemical industry due to characteristics such as its good describing property of biology and nontoxic, easily biological-degradables etc. Field.Electronegative carboxylic acid group can be with band on chitosan just on mannuronic acid and guluronic units in sodium alginate The amino of electricity forms compound polyelectrolyte by electrostatic interaction, and the usability of material can be improved in the electrostatic interaction of polyelectrolyte Energy.Moreover, the two still remains the unique biological compatibility of chitosan and sodium alginate by compound polyelectrolyte later And biological degradability.
104069536 A of Chinese invention patent CN, a kind of preparation side of sodium alginate-chitosan nanoscale medical dressing Method.Using the method for electrostatic spinning, using sodium alginate as spinning solution, contain the chitosan solution of crosslinking agent as receiving liquid, Sodium alginate fiber in spinning head is received in chitosan solution.The electrolyte attribute of chitosan makes it through electrostatic interaction suction Sodium alginate fiber is invested, fiber is crosslinked.This method improves the mechanical property of material to a certain extent.But This method, chitosan is not high as coagulating bath service efficiency, therefore, it is necessary to develop a kind of new chitosan/calcium alginate without Needle nano fibrous membrane and preparation method thereof.
Summary of the invention
In order to give full play to the application of chitosan, sodium alginate raw material on medical dressing, using needleless electrostatic spinning skill Art, by chitosan/polyethylene oxide (PEO) composite solution or Chitosan/PolyvinylpyrrolidoneHybrid Hybrid Film (PVP) composite solution, sea Mosanom/PEO composite solution or sodium alginate/PVP composite solution are respectively placed in the two sides of electrostatic spinning solution box, make two Kind solution converges at spinning head, and during the volatilization of Static Spinning solvent, sodium alginate, chitosan is made to carry out polyelectrolyte Self-crosslinking obtains a kind of polyelectrolyte that self-crosslinking chitosan/sodium alginate/PEO or chitosan/sodium alginate/PVP is formed Electrostatic spinning nano fiber composite membrane.Meanwhile in order to further enhance the service performance of material, using the calcium cross-linked method pair of chlorination Nano composite membrane is crosslinked, and is exchanged the sodium alginate for being dissolved in water with divalent calcium ions and is generated calcium alginate not soluble in water, Obtain Ah-ACMS composite Nano fibre film.Material strength prepared by the present invention is high, and service performance is good, gives full play to shell The biocompatibility of glycan, calcium alginate.
The present invention provides a kind of preparation side of medical dressing chitosan/calcium alginate needleless electrostatic spinning nano fiber film Method, specific implementation step are as follows:
(1) by the PEO aqueous solution or PVP aqueous solution of the sodium alginate aqueous solution of 1wt%~5wt% and 5wt~10wt% It is uniformly mixed with volume ratio for 1:9~5:5, obtains sodium alginate/PEO composite solution or sodium alginate/PVP composite solution;
(2) by the PEO aqueous solution of the chitosan acid solution of 1wt%~5wt% and 5wt~10wt% or PVP aqueous solution with Volume ratio is uniformly mixed for 1:9~5:5, obtains chitosan/PEO composite solution or chitosan/PVP composite solution;
(3) sodium alginate/PEO composite solution or sodium alginate/PVP composite solution and step obtained step (1) (2) chitosan/PEO composite solution or chitosan/the PVP composite solution obtained carries out needleless electrostatic spinning, can be obtained shell Glycan/sodium alginate/PEO electrostatic spinning nano fiber composite membrane or chitosan/sodium alginate/PVP electrostatic spinning nano fiber are multiple Close film;
(4) chitosan/sodium alginate/PEO electrostatic spinning nano fiber composite membrane or chitosan obtained step (3)/ Sodium alginate/PVP electrostatic spinning nano fiber composite membrane is placed in the CaCl of 3wt~6wt%2In ethanol solution be crosslinked 20min~ 30min, obtains chitosan/calcium alginate electrostatic spinning nano fiber composite membrane, and main component is chitosan/calcium alginate.
As a preferred technical solution, in step (2), chitosan acid solution the preparation method is as follows: chitosan is dissolved In 50wt% acetic acid aqueous solution, it is configured to the solution of 1wt%~5wt%.
As a preferred technical solution, in step (3), the condition of needleless electrostatic spinning are as follows: in solution box in composite solution Sodium alginate aqueous solution, chitosan acid solution and PEO aqueous solution or three kinds of liquor capacity ratios of PVP aqueous solution are 10~25:10 ~25:50~80, spinning voltage are 60~80kV, solution box 80~150mm/s of speed, the spinning time 20 minutes or more.
As a preferred technical solution, in step (3), the condition of needleless electrostatic spinning are as follows: in solution box in composite solution Sodium alginate aqueous solution, chitosan acid solution and PEO aqueous solution or three kinds of liquor capacity ratios of PVP aqueous solution are 10~25:10 ~25:50~80, spinning voltage be 60~80kV, solution box 80~150mm/s of speed, the spinning time 20 minutes~4 hours.
As a preferred technical solution, in step (3), by step (1) obtain sodium alginate/PEO composite solution or Chitosan/PEO the composite solution or chitosan that sodium alginate/PVP composite solution and step (2) obtain/PVP composite solution benefit Needleless electrostatic spinning is carried out with needleless electrostatic spinning equipment, it is multiple to can be obtained chitosan/sodium alginate/PEO electrostatic spinning nano fiber Close film or chitosan/sodium alginate/PVP electrostatic spinning nano fiber composite membrane.
The medical dressing obtained the invention further relates to the above-mentioned preparation method of Sustainable use is quiet with chitosan/calcium alginate needleless Electro spinning nanometer fiber membrane.
The invention has the advantages that:
1, the composite polyelectrolyte film prepared by the present invention is prepared by needleless electrostatic spinning equipment.Needleless Static Spinning processing effect Rate is high, can industrialized production.
2, the composite polyelectrolyte film prepared by the present invention, nanofiber film thickness uniform, controllable, microcellular structure can be to prevent The only adhesion of dressing surface and wound.
3, the nano composite membrane prepared by the present invention does not use toxic cross-linking agents, is handed over by electrostatic force and calcium chloride Connection collaboration, improves the service performance of material, and the use for avoiding crosslinking agent may cause safety in medical field and other are secondary Effect.
4, contain a large amount of calcium ion in calcium alginate, alginates can be made to be transformed into the sodium ion exchange in blood Gel, gel can provide the healing environment of wound moist, promote hyperplasia, to play good haemostatic effect, promote wound Mouth healing.The electrostatic interaction of chitosan and sodium alginate compensates for after calcium alginate becomes water-soluble sodium alginate and causes material Expect the decline of mechanical property and service performance.
Detailed description of the invention
Fig. 1 is needleless Static Spinning schematic illustration;
Needleless electrostatic spinning is the spinning process for directly forming injection stream on free fluid surface using high voltage electric field.Solution Spinning solution moves back and forth on wire electrode in box, and under high voltage electric field, free fluid surface directly forms injection on wire electrode Flow simultaneously spinning.
Fig. 2 is the SEM photograph for the nano fibrous membrane that embodiment 1 obtains;It is (b) after being crosslinked before wherein (a) is crosslinking.
Fig. 3 is the nano fibrous membrane crosslinking front and back water resistance variation that embodiment 1 obtains.Wherein, (a) uncrosslinked 0min, (b) Crosslinking 0min, (c) uncrosslinked 10min, (d) crosslinking 10min, (e) uncrosslinked 30min, (f) crosslinking 30min, (g) are uncrosslinked 40min, (h) crosslinking are for 24 hours.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with Any mode limits the present invention.
The embodiment of the present invention selects following material:
Chitosan: deacetylation 85-90%, viscosity 10g/L, under the conditions of 20 DEG C, the Chitosan powder of 50-500mpas;
Following embodiment test method and its equipment of the present invention:
Scanning electron microscope (SEM): super-resolution thermal field emission scanning electron microscope JSM-780DF, Japan Electronics JEDL;
Needleless electrostatic spinning equipment: nanometer spider silk electrostatic spinning machine, ELMARCO company of Czech;
Strength test equipment: LLY-06E type electronic mono-fiber strong force instrument, Laizhou Electron Instrument Co., Ltd..Test specimens Product manufacturing process: long 5cm, the sample of wide 2mm are cut out.It is 20 DEG C in temperature, humidity is tested under the conditions of being 65%, and each sample is surveyed Three times, it is averaged;
Thickness test equipment: YG141LA type digital textile thickness gauge, Laizhou Electron Instrument Co., Ltd..With YG141LA type digital textile thickness gauge measures the thickness of film, and every kind of film at least measures 3 data, takes its average value, as a result smart Really arrive 0.001mm;
The tensile strength calculation formula of film is as follows:
σ=F/ (100 × H × d)
In formula: σ: tensile break strength, MPa;F: pulling force when sample fracture, cN;H: the width of sample, mm;D: sample Thickness, mm.
Embodiment 1
Sodium alginate is directly dissolved in deionized water, the solution of 1wt% is configured to, in 80 DEG C of stirrings until solution is saturating It is bright;Chitosan is directly dissolved in the solution in water, being configured to 1.5wt% in 50wt% acetic acid solution, is stirred at room temperature straight It is transparent to solution;PEO is dissolved in deionized water, 8wt% solution is configured to, is stirred at room temperature until solution is transparent;It will Sodium alginate aqueous solution and PEO aqueous solution are stirred 10 hours with the mixing of volume ratio 2:8 ratio, obtain uniform sodium alginate/ PEO solution;Chitosan acid solution and PEO aqueous solution are mixed with volume ratio 5:5 ratio, stirs 10 hours, it is poly- to obtain uniform shell Sugar/PEO solution;Chitosan/PEO solution and sodium alginate/PEO solution are put in needleless Static Spinning (shown in Fig. 1) solution respectively At this time, the left and right sides (sodium alginate aqueous solution, chitosan acid solution, three kinds of PEO aqueous solution in composite solution in solution box of box Liquor capacity ratio is 10:25:65, is 60kV in spinning voltage, solution box speed 80mm/s the spinning time 25 minutes, can get Self-crosslinking chitosan/sodium alginate/PEO electrostatic spinning nano fiber composite membrane in homogeneous thickness, shown in electromicroscopic photograph such as Fig. 2 (a), Fibre diameter 150-200mm or so, film thickness 0.025mm, film stretching strength is 0.516MPa, the film weight of 4cm × 4cm size For 0.089g.Chitosan/sodium alginate/PEO electrostatic spinning nano fiber composite membrane is put on metal mesh bracket again, in crosslinking agent For 5%CaCl2It is crosslinked 30min in ethanol solution, after 80 DEG C of dryings, obtains electrostatic spinning nano fiber composite membrane, electromicroscopic photograph is such as Shown in Fig. 2 (b), main component is chitosan/calcium alginate, is crosslinked between nanofiber, has micropore, film thickness is The film weight 0.092g of 0.106mm, 4cm × 4cm size, film stretching strength is 0.712MPa.
Nano fibrous membrane after crosslinking before crosslinking is placed in deionized water, 10min, 30min, 40min is spaced, sees for 24 hours The water resistance variation of nano fibrous membrane crosslinking front and back is examined, is changed by the hydrophily that photo records sample, experimental result such as Fig. 3 institute Show.Wherein, (a) uncrosslinked 0min, (b) crosslinking 0min, (c) uncrosslinked 10min, (d) crosslinking 10min, (e) uncrosslinked 30min, (f) 30min, (g) uncrosslinked 40min, (h) crosslinking are crosslinked for 24 hours.The experimental results showed that the sample after crosslinking is in deionized water After 24 hours, original sample morphology size is still kept, and after uncrosslinked sample 30-40min, film is completely soluble in water.It is crosslinked sample The water resistance of product is far better than uncrosslinked rear sample.
Embodiment 2
Sodium alginate is directly dissolved in deionized water, the solution of 1.5wt% is configured to, stirring is until molten at 80 DEG C Liquid is transparent;Chitosan is directly dissolved in the solution in water, being configured to 2wt% in 50wt% acetic acid solution, is stirred at room temperature Until solution is transparent;PVP is dissolved in deionized water, 10wt% solution is configured to, is stirred at room temperature until solution is transparent; Sodium alginate aqueous solution and PVP aqueous solution are mixed with volume ratio 5:5 ratio, stirred 10 hours, obtain uniform sodium alginate/ PVP solution;Chitosan acid solution and PVP aqueous solution are mixed with volume ratio 3:7 ratio, stirs 10 hours, it is poly- to obtain uniform shell Sugar/PVP solution;Chitosan/PVP solution and sodium alginate/PVP solution are put in needleless Static Spinning (shown in Fig. 1) solution respectively At this time, the left and right sides (sodium alginate aqueous solution, chitosan acid solution, three kinds of PVP aqueous solution in composite solution in solution box of box Liquor capacity ratio is 25:15:60, is 80kV in spinning voltage, solution box speed 100mm/s the spinning time 30 minutes, can get Self-crosslinking chitosan/sodium alginate/PVP electrostatic spinning nano fiber composite membrane in homogeneous thickness, nanofiber diameter 150-200mm Left and right, film thickness 0.109mm, film strength is 0.635MPa.Electrostatic spinning nano fiber/PVP electrostatic spinning nano fiber is compound Film is put on metal mesh bracket, and being put in crosslinking agent is 3%CaCl2It is crosslinked 30min in ethanol solution, obtains electrostatic spinning nano fiber Composite membrane, main component be chitosan/calcium alginate, after 80 DEG C of drying, film thickness 0.110mm, film strongly be 0.748MPa。
Embodiment 3
Sodium alginate is directly dissolved in deionized water, the solution of 2wt% is configured to, in 80 DEG C of stirrings until solution is saturating It is bright;Chitosan is directly dissolved in the solution in water, being configured to 1.5wt% in 50wt% acetic acid solution, is stirred at room temperature straight It is transparent to solution;PEO is dissolved in deionized water, 8wt% solution is configured to, is stirred at room temperature until solution is transparent;It will Sodium alginate aqueous solution and PEO aqueous solution are stirred 10 hours with the mixing of volume ratio 1:9 ratio, obtain uniform sodium alginate/ PEO solution;Chitosan acid solution and PEO aqueous solution are mixed with volume ratio 1:9 ratio, stirs 10 hours, it is poly- to obtain uniform shell Sugar/PEO solution;Chitosan/PEO solution and sodium alginate/PEO solution are put in the left and right two of needleless Static Spinning solution box respectively At this time, side (three kinds of sodium alginate aqueous solution, chitosan acid solution, PEO aqueous solution liquor capacity ratios in composite solution in solution box It is 80kV in spinning voltage, solution box speed 80mm/s the spinning time 50 minutes, can get in homogeneous thickness for 10:10:80) Self-crosslinking chitosan/sodium alginate/PEO electrostatic spinning nano fiber composite membrane, nanofiber diameter 150-200mm or so, film thickness Degree is 0.116mm, and film strength is 0.726MPa.Chitosan/sodium alginate/PEO electrostatic spinning nano fiber composite membrane is put in again It is 5%CaCl in crosslinking agent on metal mesh bracket2It is crosslinked 30min in ethanol solution, obtains electrostatic spinning nano fiber composite membrane, Its main component is chitosan/calcium alginate, and after 80 DEG C of dryings, film thickness 0.115mm, film strength is 0.844MPa.

Claims (4)

1. a kind of medical dressing chitosan/calcium alginate needleless electrostatic spinning nano fiber film preparation method, which is characterized in that Include the following steps:
(1) by the polyethylene oxide aqueous solution or polyethylene pyrrole of the sodium alginate aqueous solution of 1wt%~5wt% and 5~10wt% Pyrrolidone aqueous solution is uniformly mixed with volume ratio for 1:9~5:5, obtains sodium alginate/polyethylene oxide composite solution or seaweed Sour sodium/polyvinylpyrrolidone composite solution;
(2) by the polyethylene oxide aqueous solution or polyvinyl pyrrole of the chitosan acid solution of 1wt%~5wt% and 5~10wt% Alkanone aqueous solution is uniformly mixed with volume ratio for 1:9~5:5, obtain chitosan/polyethylene oxide composite solution or chitosan/ Polyvinylpyrrolidone composite solution;
(3) sodium alginate/polyethylene oxide composite solution or sodium alginate/polyvinylpyrrolidone for obtaining step (1) The chitosan that composite solution is obtained with step (2)/polyethylene oxide composite solution or Chitosan/PolyvinylpyrrolidoneHybrid Hybrid Film are compound Solution carry out needleless electrostatic spinning, can be obtained chitosan/sodium alginate/polyethylene oxide electrostatic spinning nano fiber composite membrane or Person's chitosan/sodium alginate/polyvinylpyrrolidone electrostatic spinning nano fiber composite membrane;
(4) chitosan/sodium alginate/polyethylene oxide electrostatic spinning nano fiber composite membrane or shell obtained step (3) is poly- Sugar/sodium alginate/polyvinylpyrrolidone electrostatic spinning nano fiber composite membrane is placed in the CaCl of 3wt~6wt%2In ethanol solution It is crosslinked 20min~30min, obtains chitosan/calcium alginate electrostatic spinning nano fiber composite membrane.
2. preparation method according to claim 1, in step (4), the condition of needleless electrostatic spinning are as follows: compound in solution box Sodium alginate aqueous solution, chitosan acid solution and polyethylene oxide aqueous solution or aqueous povidone solution three in solution Kind of liquor capacity ratio is 10~25:10~25:50~80, and spinning voltage is 60~80kV, solution box 80~150mm/s of speed, The spinning time 20 minutes or more.
3. preparation method according to claim 1, in step (2), chitosan acid solution the preparation method is as follows: shell is gathered Sugar is dissolved in 50wt% acetic acid aqueous solution, is configured to the solution of 1wt%~5wt%.
4. the medical dressing that the preparation method as described in any one of claim 1-3 obtains with chitosan/calcium alginate without Needle electrostatic spinning nano fiber film.
CN201811385922.3A 2018-11-20 2018-11-20 Chitosan/calcium alginate needle-free electrostatic spinning nanofiber membrane for medical dressing and preparation method thereof Active CN109267240B (en)

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CN111020745A (en) * 2019-12-31 2020-04-17 泰州市榕兴医疗用品股份有限公司 Preparation method of sodium alginate and chitosan composite nanofiber
CN112206342A (en) * 2020-09-27 2021-01-12 广东泰宝医疗科技股份有限公司 Alginate composite dressing and preparation method thereof
CN112760811A (en) * 2020-12-30 2021-05-07 中国热带农业科学院南亚热带作物研究所 Chitosan-alginate composite nanofiber membrane and preparation method and application thereof
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CN114447424A (en) * 2022-01-29 2022-05-06 杭州阳名新能源设备科技有限公司 Solid electrolyte and preparation method and application thereof
CN114447424B (en) * 2022-01-29 2024-02-13 杭州阳名新能源设备科技有限公司 Solid electrolyte and preparation method and application thereof
CN115778827A (en) * 2023-02-02 2023-03-14 广东碧茜生物科技有限公司 high-VC-loading core/shell type nanofiber mask and preparation method and application thereof

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