KR20100133117A - Nanofiber for dressing, dressing composite using the same, and method of manufacturing the same - Google Patents
Nanofiber for dressing, dressing composite using the same, and method of manufacturing the same Download PDFInfo
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- KR20100133117A KR20100133117A KR1020090051831A KR20090051831A KR20100133117A KR 20100133117 A KR20100133117 A KR 20100133117A KR 1020090051831 A KR1020090051831 A KR 1020090051831A KR 20090051831 A KR20090051831 A KR 20090051831A KR 20100133117 A KR20100133117 A KR 20100133117A
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- dressing
- nanofiber
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- nanofibers
- cationic polymer
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/225—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- Hematology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
The present invention relates to a dressing nanofibers, a dressing composite using the same and a method for manufacturing the same, in particular, cationic polymer nanofibers and anionic polymer nanofibers are self-crosslinked by an ionic bond in an aqueous environment without the addition of a crosslinking agent and thus gel (gel). The present invention relates to a dressing nanofiber, a dressing composite using the same, and a method for manufacturing the same, which are used for the treatment of wounds such as wounds, burns and bedsores.
Dressing is a method used to improve the healing rate by covering the wound surface, which is the site of skin defects caused by burns, wounds, bedsores and traumas. Since the announcement that it is twice as fast as the environment, wet dressing has been developed and released one after another, and there are various ways to treat wounds.
Wet dressing is to keep the wound surface wet and to maintain the wet state. Various hydrophilic and hydrophobic polymers are developed and combined to form a film, a sheet, a nonwoven fabric, and a sponge foam. ), It is rapidly developing into various forms such as lopes, pellets, and powders.
The material used for the healing of wounds is a product that can absorb and contain a large amount of exudates discharged from the wound surface, and should have the form of a three-dimensional network structure formed by crosslinking of hydrophilic polymers by covalent or non-covalent bonds. Due to its hydrophilicity, it should swell by absorbing a large amount of water in an aqueous solution and in an aqueous environment, but not dissolving by a crosslinked structure.
Therefore, various methods have been proposed according to the components or preparation methods, but physical crosslinking by non-covalent bonds is likely to cause deterioration of physical properties, and chemical crosslinking is known to have skin toxicity by crosslinking agents. There is a method such as, but there is a limit of equipment and high cost is a realistic situation.
In particular, it is important to have a structure in which the part in contact with the skin should be smoothly peeled off during the dressing agent exchange, and the secondary infection such as bacteria does not occur. In order to develop a dressing agent having such a property, a support having a maximized surface area is required, and it is desirable to provide a dressing agent that helps rapid transfer of exudates at the wound site and repair of the wound.
Recently, Korean Patent No. 10-0588228 describes a wound coating agent using hydrophilic nanofibers containing protein components in polyester nanofibers, and Patent No. 10-0791039 discloses a dressing agent containing an antioxidant. The manufacturing method is described. In the case of the above patents, the specific surface area to volume is excellent by using nanofibers, and the healing rate is improved by administering drugs such as protein-containing nanofiber layers and antioxidants, but it is natural polyester and bio By using a suitable polymer, it is difficult to secure sufficient mechanical properties, and it is expected to have problems such as absorption of exudates and a decrease in strength. In particular, in the case of nanofibers made of hydrophilic polymers, the surface area is maximized, so that it is difficult to maintain the fibrous structure by dissolving at the same time as water contact in an aqueous environment, so that the crosslinking treatment must be performed by chemical or physical method.
Therefore, the inventors of the present invention find that the electrospinning technique can be used to self-crosslink in an aqueous environment to form a gel and maximize the surface area of the dressing nanofibers, thereby reducing the pain of patients accompanying dressing agent replacement. It was.
The present invention has been made in order to solve the problems of the prior art as described above, the object is that the self-crosslinking in an aqueous environment is made by using a cationic polymer and an anionic polymer having biocompatibility and having biocompatibility A nanofiber for dressing and a method of manufacturing the same are provided.
Another object of the present invention is that the cationic polymer nanofibers and the anionic polymer nanofibers are self-crosslinked by ionic bonding to form a gel state in an aqueous environment without the addition of a crosslinking agent. To provide a dressing composite comprising self-crosslinked nanofibers that can minimize the pain of the accompanying patient.
Still another object of the present invention is to prepare functional nanofibers for dressings, burns, bedsores, and wounds by preparing antimicrobial agents and / or antibiotics in a spinning solution when the nanofibers for dressing are prepared by spinning. And it relates to a dressing composite using the same and a method for producing the same.
It is another object of the present invention to provide a dressing composite and a method of manufacturing the same, which facilitates laminating the dressing support and the lamination, and can be mass-produced at low cost.
Another object of the present invention relates to a swellable wet dressing nanofiber in which a cationic polymer nanofiber and an anionic polymer nanofiber are self-crosslinked by an ionic bond to form a hydrogel in an aqueous environment.
In order to achieve the above object, the present invention is characterized in that the cationic polymer and the anionic polymer is mixed spinning and made of a composite nanofiber web, and self-crosslinked by ionic bonding in an aqueous environment to form a hydrogel Provided are nanofibers for self-crosslinking dressings.
According to another feature of the present invention, the present invention consists of a nanofiber web is a random composite of the first nanofibers made of cationic polymer and the second nanofibers made of anionic polymer, the first and second nanofibers The self-crosslinked dressing nanofibers, characterized in that the self-crosslinked by the ionic bonds in an aqueous environment to form a hydrogel.
According to another feature of the invention, the present invention comprises a dressing support, and a nanofiber web laminated on one side of the dressing support and a composite of the spinning and the cationic polymer and anionic polymer, the nanofiber is aqueous It provides a dressing assembly, characterized in that to form a hydrogel under the environment.
According to another feature of the present invention, the present invention is a nanofiber of which the dressing support, the first nanofiber made of a cationic polymer and the second nanofiber made of anionic polymer are stacked on one side of the dressing support And a web, wherein the first and second nanofibers form a hydrogel in an aqueous environment.
According to another feature of the invention, the present invention comprises the steps of dissolving a cationic polymer and an anionic polymer, respectively, to prepare a first and a second spinning solution, by mixing and spinning the first and second spinning solution to the cation It provides a method for producing a nanofiber for dressing, comprising the step of obtaining a nanofiber web is a composite of an ionic polymer and an anionic polymer.
According to another feature of the invention, the present invention comprises the steps of preparing a first and a second spinning solution by dissolving a cationic polymer and an anionic polymer, respectively, by spacing the first and second spinning solution separately at intervals It provides a method for producing a nanofibers for dressing comprising the step of obtaining a nanofiber web of the first nanofibers made of the cationic polymer and the second nanofibers made of anionic polymer are randomly complexed.
The first and second spinning solution may further include a fiber forming polymer, and the first and second spinning solution may each contain 10 to 90 wt% of the fiber forming polymer.
The cationic polymer is made of any one of chitosan, chitooligomer, PEI, polystylene divinylbenzene copolymer, and the anionic polymer is preferably made of any one of PAA, collagen, gelatin, and hyaluronic acid.
In addition, it is preferable that the ratio of the cationic polymer material and the anionic polymer material is adjusted and mixed at a ratio of 10 to 90:90 to 10%. This is determined by self-crosslinking in an aqueous environment, but if one polymer is less than 10% or more than 90%, the crosslinking degree is weak, so that water absorption and transport cannot be controlled smoothly, and there are many dissolved parts. Limits arise.
The dressing support may be selected from the group consisting of a urethane foam, a hydrogel type, a hydrofiber type, a nonwoven fabric type, a silver nano-containing nonwoven fabric, a superabsorbent resin, and the like. Depending on the condition of the patient and the size of the wound, it can be used in various ways.
The nanofibers may further comprise a fiber-forming polymer, wherein the fiber-forming polymer is from the group consisting of polyvinyl alcohol (PVA), polyacrylonitrile (PAN), PU, PMMA, PLA, PGA, PLGA, PVP, and PS It is preferable that it is comprised by combining the selected polymer individually or in combination. The fiber moldable polymer is not limited to a specific material, and is preferably a material having spinning compatibility.
In addition, the spinning method may be any one of electrospinning, electrospray, electrobrown spinning, centrifugal electrospinning, and flash electroelectrospinning. It is preferable to use.
Furthermore, the present invention may further include mixing an antimicrobial substance or an antibiotic substance with the first and second spinning solutions.
The present invention also provides a dressing composite, which is prepared by laminating self-crosslinked nanofibers spun in the form of a nonwoven fabric and an existing dressing agent.
Since the cationic polymer material and the anionic polymer material have biocompatibility, the self-crosslinked nanofibers obtained using them also have biocompatibility.
Accordingly, in the present invention, nanofibers obtained by using a cationic polymer and an anionic polymer having self-crosslinking under an aqueous environment and having biocompatibility also have biocompatibility.
In addition, the swellable wet dressing composite including the self-crosslinked nanofiber according to the present invention is a cationic polymer nanofiber and anionic polymer nanofibers are self-crosslinked by ionic bonding in an aqueous environment without the addition of a crosslinking agent to form a gel state, When the dressing complex is replaced, the dressing support may be separated by only removing the dressing support, thereby minimizing the pain of the patient.
Furthermore, in the present invention, when the nanofibers for dressing are manufactured by spinning, the antimicrobial agent and / or antibiotics are mixed with the spinning solution to prepare wounds, burns, bedsores and the like.
In addition, the dressing composite of the present invention can be easily mass-laminated with the existing dressing agent used as a dressing support mass production can be made at a low cost.
In the dressing composite including the self-crosslinked nanofiber according to the present invention, the cationic polymer nanofiber and the anionic polymer nanofiber are self-crosslinked by ionic bonding in an aqueous environment to form a hydrogel to maintain a wet state. Therefore, it creates an environment favorable for the regeneration of the affected area.
In addition, the present invention is capable of easily adding and complexing various materials in the spinning solution to easily control the antimicrobial function and the degree of crosslinking, which is applicable to various fields.
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The self-crosslinked nanofiber nonwoven fabric according to the present invention first prepares a solution in a concentration capable of spinning a cationic polymer and an anionic polymer, respectively, and is prepared by a spinning method using a Y-type nozzle or a double nozzle, and a dressing support. The lamination method is used to prepare the dressing complex for wound treatment. Hereinafter, each step will be described in detail.
A. Step of preparing spinning solution containing cationic and anionic polymer
Prepare a spinning solution by dissolving a cationic polymer and an anionic polymer at a spinnable concentration using a suitable solvent.
In the present invention, the cationic polymer material is chitosan, chitooligomer, PEI, polystyrene divinylbenzene copolymer, etc., and the anionic polymer material is PAA, collagen, gelatin, hyaluronic acid, or the like, respectively. It can be used in combination with a fibrous forming polymer material. The cationic polymer material and the anionic polymer material are each mixed with an appropriate ratio of the fibrous forming polymer, and then stirred and dissolved at an irradiable concentration by using a compatible solvent. The first and second spinning solutions mixed with the fibrous forming polymer are prepared.
In the preparation of the first spinning solution, the content of the cationic polymer material is suitably about 10 to 90% by weight relative to the fiber moldable polymer material. The reason for this is that when the content of the cationic polymer material is less than 10% by weight, the self-crosslinking rate is low, and when it exceeds 90% by weight, it is difficult to form fibers due to poor spinning properties.
In addition, in the preparation of the second spinning solution, the content of the anionic polymer material is also about 10 to 90% by weight relative to the fiber moldable polymer material for the same reason as the cationic polymer material.
B. Polymer Nanofiber Forming Step
The prepared first and
In this case, the nozzle used for electrospinning may use a Y-shaped
In the Y-shaped
The Y-shaped
In the electrospinning, the voltage can be adjusted from 0.5 kV to 100 kV, and the
In addition, the distance between the spin pack and the collector plate is preferably adjusted to 5 to 50 cm. The discharge amount during spinning is discharged at a discharge rate of 0.01 ~ 5cc / hole min per hole using a metering pump, it is preferable to emit in an environment of 10-90% relative humidity in the chamber that can control the temperature and humidity during spinning.
As described above, when the first and
In addition, when the first and
C. Dressing Support / Self-crosslinked Nanofiber Lamination and Sterilization Step
In the present invention, by using the conventional dressing agent as a
The self-crosslinked
The dressing
The dressing
As a result, the
In the present invention, when the
Furthermore, in the present invention, when the dressing
Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention by these examples.
Example 1
The self-crosslinked nanofiber according to the present invention was dissolved by mixing 50:50 parts by weight of a cationic polymer, chitooligomer, and polyvinyl alcohol (polyvinylachol (PVA)) to 10% by weight of the solvent water. Further, PAA (polyacrylicacid) and PAN (polyacrylonitrile), which are anionic polymers, were mixed at 50:50 parts by weight, respectively, and dissolved in 10 parts by weight of DMF as a solvent.
Each spinning solution prepared by the above method was spun using a Y-type nozzle as shown in FIG. At this time, the applied voltage was 25 kV, the distance between the spinneret and the
2 is a scanning electron micrograph of a nanofiber according to Example 1 prepared by an electrospinning method using a Y-type nozzle and the cationic polymer and the anionic polymer are combined, (a) 1k, (b) 5k, ( c) 10k x magnification photo. As shown in FIG. 2, the fiber diameter was mostly less than 1 μm, indicating an average of 500 nm.
[Example 2]
The spinning solution prepared in the same manner as in Example 1 was subjected to spinning in the same manner as in Example 1 using a double nozzle as shown in FIG. 1C.
3 shows a scanning electron micrograph of a self-crosslinked nanofiber prepared using a double nozzle. FIG. 3 is a scanning electron micrograph of a nanofiber in which a cationic polymer and an anionic polymer are manufactured by a double nozzle as a second embodiment of the present invention; FIG. (a) 1k, (b) 5k, (c) 10k x magnification photographs.
Figure 4 is a photograph of the self-crosslinking in the aqueous environment of the nanofibers prepared by the second embodiment of the present invention; (a) A photograph showing the state of self-crosslinking while adsorbing water in an aqueous environment, and (b) A photograph showing the formation of gelation by self-crosslinking.
As shown in Figure 4 (b), it can be seen that when exposed to an aqueous environment, the nanofiber nonwoven fabric according to the present invention is self-crosslinked while absorbing moisture without decomposing.
In addition, FIG. 5 shows the results of differential thermal analysis (DSC) of chitooligomer, PAA, and crosslinked chitooligomer / PAA. As a result of DSC analysis in the air, it was found that the crystallization proceeded rapidly by the crosslinking treatment in the case of the chitooligomer / PAA, compared to the chitooligomer or PAA which was not crosslinked.
Example 3
The self-crosslinked nanofibers prepared in Example 2 and Aquacel Ag manufactured by ConvaTec Co., Ltd. were bonded to each other at 100 ° C. using a lamination apparatus, to form a dressing assembly in which the self-crosslinked nanofibers and the existing dressing agent were bonded to the dressing support. Prepared.
6A and 6B show photographs of the dressing assembly for adsorbing moisture in a lamination and aqueous environment. Figure 6a is a composite photo by lamination of the self-crosslinked nanofibers prepared by the third embodiment of the present invention and the existing dressing agent, Figure 6b is a photograph showing the absorption of water in an aqueous environment to form a gel.
Figure 7 is a picture showing the exchange of the dressing agent, it can be seen that the self-crosslinked nanofibers are removed only the dressing support, which is the existing dressing agent while maintaining the state attached to the skin.
Comparative Example 1
For comparison, chito oligomer and PVA were mixed and prepared in the same manner as in Example 1, and electrospinning was performed alone. In this case, the average diameter of the prepared nanofibers was about 200 nm, and FIG. 8 showed that nanofibers made of chitooligomer and PVA were directly decomposed by a high specific surface area when contacted in an aqueous environment.
Figure 8 is prepared by the comparative example (a) water-soluble polymer nanofibers photo, (b) a picture that is dissolved immediately upon contact with the aqueous environment, (c) a picture that is dissolved and cut immediately upon contact with the aqueous environment.
The present invention is applied to a dressing assembly that can reduce the pain of patients involved in dressing nanofibers as a dressing nanofibers that are self-crosslinked in an aqueous environment using an electrospinning technique to form a gel and maximize the surface area.
Figure 1a to 1c is a development view showing the configuration of the present invention, (a) a schematic diagram of the cationic polymer nanofibers and anionic polymer nanofibers are self-crosslinked by exudates during wound healing, (b) nano using a Y-type nozzle Fiber manufacturing method, (c) schematic diagram for manufacturing nanofibers using the upper and lower double nozzles,
FIG. 2 is a scanning electron micrograph of a nanofiber in which a cationic polymer and an anionic polymer are manufactured using a Y-type nozzle of an embodiment of the present invention; FIG. (a) 1k, (b) 5k, (c) 10k x magnification,
3 is a scanning electron micrograph of a nanofiber in which a cationic polymer and an anionic polymer are manufactured by an upper and lower double nozzles according to one embodiment of the present invention; (a) 1k, (b) 5k, (c) 10k x magnification,
Figure 4 is a photograph of the self-crosslinking in the aqueous environment of the nanofibers prepared by one embodiment of the present invention; (a) a photo showing the state of self-crosslinking while adsorbing water in an aqueous environment, (b) a photo forming gelation by self-crosslinking,
Figure 5 is a differential scanning thermal analysis graph (DSC) of the nanofibers prepared by one embodiment of the present invention,
Figure 6a is a composite photo by lamination of the self-crosslinked nanofibers prepared according to an embodiment of the present invention and the existing dressing agent, Figure 6b is a photograph showing the absorption of water in an aqueous environment to form a gel,
7 is a photograph showing a state in which the nanofibers of the present invention are present on the skin and only the existing dressing agent is removed when the dressing is removed.
Figure 8 is a (a) water-soluble polymer nanofibers prepared by the comparative example, (b) a picture that is directly dissolved when contacting the aqueous environment, (c) is a picture that is dissolved and cut immediately upon contact with the aqueous environment.
DESCRIPTION OF THE REFERENCE NUMERALS
10a, 10b: Spinning solution 12: Y-type nozzle
14,14a, 14b: dual nozzle 16: current collector
18: high voltage regulator 20: dressing assembly
20a: hydrogel 22: nanofiber
24: dressing support 30: wound surface
32: skin 34: exudate
Claims (18)
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102115918A (en) * | 2011-03-13 | 2011-07-06 | 东华大学 | Preparation method of superfine oriented polymer fibers through stable jet-flow electrically driven spinning |
WO2011159666A2 (en) * | 2010-06-14 | 2011-12-22 | Samuel Brian Peterson | Therapeutic heat-transfer pack |
WO2015174643A1 (en) * | 2014-05-15 | 2015-11-19 | 포항공과대학교 산학협력단 | Hydrogel containing surface-treated nanofibers and method for preparing same |
CN108601860A (en) * | 2016-02-12 | 2018-09-28 | 金珂生物医疗公司 | Chitosan ultrafine fiber system |
WO2019059631A1 (en) * | 2017-09-20 | 2019-03-28 | 차의과학대학교 산학협력단 | Coacervate composition containing protein drug and wound healing agent comprising same |
CN110316698A (en) * | 2019-07-08 | 2019-10-11 | 陕西科技大学 | A kind of one-dimensional hydrogen storage material of PMMA organic coating nanometer Mg and preparation method thereof |
KR20200018140A (en) * | 2018-08-10 | 2020-02-19 | 강원대학교산학협력단 | Alginate hydrogel containing nanofibers adsorbed metal nanoparticles having antibacterial, and use thereof method for the preparation thereof |
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2009
- 2009-06-11 KR KR1020090051831A patent/KR20100133117A/en not_active Application Discontinuation
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011159666A2 (en) * | 2010-06-14 | 2011-12-22 | Samuel Brian Peterson | Therapeutic heat-transfer pack |
WO2011159666A3 (en) * | 2010-06-14 | 2012-04-26 | Samuel Brian Peterson | Therapeutic heat-transfer pack |
CN102115918A (en) * | 2011-03-13 | 2011-07-06 | 东华大学 | Preparation method of superfine oriented polymer fibers through stable jet-flow electrically driven spinning |
CN102115918B (en) * | 2011-03-13 | 2013-08-07 | 东华大学 | Preparation method of superfine oriented polymer fibers through stable jet-flow electrically driven spinning |
WO2015174643A1 (en) * | 2014-05-15 | 2015-11-19 | 포항공과대학교 산학협력단 | Hydrogel containing surface-treated nanofibers and method for preparing same |
CN108601860A (en) * | 2016-02-12 | 2018-09-28 | 金珂生物医疗公司 | Chitosan ultrafine fiber system |
WO2019059631A1 (en) * | 2017-09-20 | 2019-03-28 | 차의과학대학교 산학협력단 | Coacervate composition containing protein drug and wound healing agent comprising same |
US11541151B2 (en) | 2017-09-20 | 2023-01-03 | Cha University Industry-Academic Cooperation Foundation | Coacervate composition containing protein drug and wound healing agent comprising same |
KR20200018140A (en) * | 2018-08-10 | 2020-02-19 | 강원대학교산학협력단 | Alginate hydrogel containing nanofibers adsorbed metal nanoparticles having antibacterial, and use thereof method for the preparation thereof |
CN110316698A (en) * | 2019-07-08 | 2019-10-11 | 陕西科技大学 | A kind of one-dimensional hydrogen storage material of PMMA organic coating nanometer Mg and preparation method thereof |
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