CN106512081A - Spraying type aqueous chitosan wound dressing - Google Patents
Spraying type aqueous chitosan wound dressing Download PDFInfo
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- CN106512081A CN106512081A CN201611115634.7A CN201611115634A CN106512081A CN 106512081 A CN106512081 A CN 106512081A CN 201611115634 A CN201611115634 A CN 201611115634A CN 106512081 A CN106512081 A CN 106512081A
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- shitosan
- wound dressing
- aqua
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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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0023—Polysaccharides
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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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a spraying type aqueous chitosan wound dressing, which belongs to the technical field of the medical wound dressing. The spraying type aqueous chitosan wound dressing comprising chitosan, glycerinum, carbon dioxide, and distilled water is stored into a high-pressure-resistant container bottle with a nozzle in a canning mode. Because a carbon-dioxide aqueous solution is used as a solvent for chitosan, the potential hazard on the health of a user by the acid residual in the used chitosan film can be eliminated. Moreover, the prepared chitosan film has the excellent water-resistant performance and high air permeability and flexibility; and when the spraying type aqueous chitosan wound dressing is used, wound healing can be accelerated.
Description
Technical field
The present invention relates to a kind of spary coating type shitosan aqua wound dressing, belongs to medical wound dressing technical field.
Background technology
Skin has the invasion of the external pathogenetic bacteria of opposing, drains human body waste, prevents body water evaporation to scatter and disappear, adjusts
Human body temperature, experiences the critical function of environmental stimuli.Because wound, abrade, burn and fester etc. cause skin damage when, hold very much
Easily cause locally even systemic problems, such as moisture and protein excessively scatter and disappear, immune system disorder, bacterium infection etc., seriously
Even threat to life.Therefore, need using wound dressing to accelerate to stop blooding, protect the surface of a wound, prevent bacterium sense during skin damage
Dye, and the suitable repairing environment of wound is created, accelerate wound healing.Traditional wound dressing is mainly gauze, absorbent cotton, bandage
Deng, do not possess treatment and repair the performances such as wound, there is no antibacterial activity yet, in clinic, range of application is limited to.Thus,
Wound healing, the easy to use and novel wound dressing with multiple efficacies such as antibacterials can be promoted gradually to grow up.
Shitosan is a kind of native amino polysaccharide that de-acetyl chitin is obtained, and is that amount is only second to fiber on the earth
The polysaccharide of element, superior performance, with biodegradable, biocompatibility and antimycotic, antiallergy, antitumor and immune activation
The physiologically actives such as effect.Shitosan can promote cell propagation, tissue growth and blood clotting, mitigate god for wound process
The pain of Jing ends;Additionally, shitosan has good hydrophily, the wetness degree that wound can be kept certain accelerates downright bad group
Knit and fibrinous dissolving, be conducive to cell proliferation and differentiation and movement, accelerate the formation of granulation tissue, promote healing for wound
Close.Therefore, chitosan-based wound dressing obtains the extensive concern of people.
China Patent Publication No. is 1493364 A of CN, and publication date is on May 5th, 2004, entitled shitosan life
Shitosan to be made respin after silk and is made into gauze by the manufacture method of thing dressing, this application case, then applies molecular weight on gauze again
Shitosan less than 5000, is obtained chitin biodressing.China Patent Publication No. is 1887358 A of CN, and publication date is 2007
On January 3, a kind of entitled medical chitosan dressing and its application, this application case with shitosan and Chinese medical extract or
Chitosan derivatives or metal ion are mixed and made into powdered chitosan dressing according to a certain percentage, or will be each in the powdery dressing
Composition mixes according still further to certain proportion after first each dissolving, then by knifing, be dried to obtain membrane-like chitosan dressing, it is also possible to
Above-mentioned mixed solution is obtained into spongy chitosan dressing by freeze-drying.China Patent Publication No. is CN 103656731
A, publication date is on March 26th, 2014, a kind of entitled medical chitosan combine dressing, and this application case is by shitosan, sea
Alginates, antiseptic and antiphlogistic are mixed to get powdered chitosan combine dressing according to a certain percentage, or by powdered chitosan
Combine dressing is fully dissolved in adding acetic acid aqueous solution, pours in masking mould, strike off after adding plasticizer, after being dried, is taken off
Mould, is obtained membranaceous shitosan combine dressing.China Patent Publication No. is 104324412 A of CN, and publication date is 2 months 2015 4
Day, chitin fiber and bamboo fibre are passed through needling shape by a kind of entitled bamboo protoconch glycan functional dressing, this application case
Into the dressing basic unit of nonwoven fabric construct, then dressing basic unit lower surface patch skin layers using high molecular polymer as antiseepage film
Layer, dressing basic unit upper surface is the water lock layer being made up of strong water-absorption fiber.China Patent Publication No. is 104623719 A of CN, public
Day is opened on May 20th, 2015, entitled a kind of aquagel dressing and preparation method thereof, this application case is by low point
The shitosan of son amount is dissolved in acetic acid solution, is subsequently adding Alose, skin penetration enhancer, anti-hemorrhagic compound etc., and is passed through
Glutaraldehyde cross-linking, is obtained aquagel, then Jing is washed, dried, stripping and slicing, sterilizing obtain aquagel dressing.
Shitosan wound dressing prepared by foregoing invention mostly is powdery, membranaceous, spongy, fabric construction shape or gelinite knot
Structure shape, on extensive wound face and body part wound face in-convenience in use, and dressing is poor with the adhesion of wound, needs
Wound top layer to be sticked to by external force such as adhesive plasters, there are problems that being inconvenient to storing, carry and.In order to overcome above-mentioned asking
Topic, China Patent Publication No. is 102671232 A of CN, and publication date is September in 2012 19, and entitled tourmaline/shell gathers
Sugared hydrochloride composite spraying type aqua dressing and preparation method thereof, this application case is dissolved in chitosan hydrochloride in deionized water to be made
Solution is obtained, tourmaline powder is subsequently adding, is uniformly mixed, add the mixing of polyvinylpyrrolidone (PVP) ethanol solution equal
It is even, obtain Tourmaline/chitosan hydrochloride compound spray-type aqua wound dressing.China Patent Publication No. is CN 102847193
A, publication date are on January 2nd, 2013, and a kind of entitled chitosan fluid dressing film, this application case are dissolved chitosan in
In acid solution, the gelatin water-swellable with Jing mixes, and adds glycerine and silver salt solution, and the effect of Jing ultrasonic waves obtains fluid dressing
Film.
As the relative molecular mass of shitosan is larger, and intermolecular there is stronger Hyarogen-bonding, chemical property
Stable, dissolubility is poor, it is impossible in being directly dissolved in water or in general organic solvent, so existing disclosed technical scheme is adopted
With the dilute acid soln dissolving shitosan of the organic or inorganics such as acetic acid, hydrochloric acid, citric acid.Thus obtained shitosan aqua dressing,
The healing of wound by the evaporation of moisture, in wound surface film forming, can be promoted.But film formation time is longer, and due to being formed
Chitosan film in have acid residual, meet water can dissolve again, cause its poor water resistance.In addition, the residual of chemical substance, to people
Body has potential health hazard.
The content of the invention
For above-mentioned problem, it is an object of the invention to provide a kind of easy to use, no chemical residue
And the fast spary coating type shitosan aqua wound dressing of film forming speed, mainly by shitosan is made water gel, Ran Houjun
It is even to be dispersed in distilled water, carbon dioxide is continually fed under the conditions of high pressure low temperature, chitosan solution is obtained, then it is irradiated
Sterilizing, it is canned, obtain spary coating type shitosan aqua wound dressing.
Dissolving of the chitosan gel rubber in arbon dioxide solution can be represented with below formula:
First, carbon dioxide solubility produces carbonic acid in water, and carbonic acid can ionize out a H with point+, while shell is poly-
Sugared gel water absorption in whose solution is big, H+Chitosan gel rubber is provided easy access to, while be attached on shitosan, it is solvable so as to obtain
Chitosan-NH3 +。
Spary coating type shitosan aqua wound dressing prepared by the inventive method, is painted on wound surface during use, can
With in wound surface fast filming, and keep wound in the environment of moistening, promote wound healing, it is to avoid wrapping, combination property
It is superior, there is good application prospect in terms of wound repair.
To achieve these goals, its technical solution is:
A kind of spary coating type shitosan aqua wound dressing, the shitosan aqua wound dressing are stored in high-pressure bottle,
Spary coating type shitosan aqua wound dressing is made up of shitosan, glycerine, carbon dioxide and distillation aqueous systems, the matter of each component
Amount percentage composition is respectively:
The viscosity-average molecular weight (M η) of described shitosan is 50000~100000, deacetylation >=90%.
Described spary coating type shitosan aqua wound dressing is dissolved in arbon dioxide solution by aquagel
Prepare.
Carbon dioxide is continually fed into distilled water by the present invention, and carbon dioxide forms carbonic acid in being dissolved in distilled water
Solution, prepares chitosan solution by solvent of this solution, and the shitosan aqua wound dressing of the present invention is stored in high-pressure bottle,
Due to keeping elevated pressures, so as to promote carbon dioxide more can be dissolved in water, so as to promote the dissolving of shitosan,
In preparation process, shitosan during dissolving is chitosan gel rubber, due to the structure disperses of the shitosan of gel state, is easily absorbed
Moisture, carbon acid solution are easier to contact with shitosan, readily facilitate the dissolving of shitosan.Chitosan solution spray prepared by the method
When being coated in wound surface, carbon dioxide volatilizees immediately, is dissolved in shitosan rapid precipitation therein and separates out to form gel mould;
Anacidity agent residual in the chitosan gel rubber film of formation, with preferable resistance to water, and the chitosan gel rubber film for being formed can be carried
For the environment of wound moist, promote wound healing.The molecular weight of shitosan has large effect to its performance, and molecular weight is higher,
Dissolving in arbon dioxide solution is more difficult, but the viscosity of solution is larger, and the mechanical property for forming chitosan film is preferable.
The present invention adopts viscosity-average molecular weight (M η) for 50000~100000, and the shitosan of deacetylation >=90% is raw material, both be ensure that
Dissolving of the shitosan in carbon acid solution, while the chitosan solution moderate viscosity for preparing, can stick together in wound surface, will not
Flow to surrounding, and the chitosan film for being formed has excellent mechanical property.In addition, in shitosan film forming procedure, the aqua
Glycerine in dressing is attached to chitosan molecule surface, hinders chitosan molecule to form the structure of densification, it is ensured that the antibacterial of formation
Film has good gas permeability, pliability, improves the comfort of patient.
Pressure in described high-pressure bottle is 0.1-0.5MPa.
Carbon dioxide dissolving in the solution can be promoted under conditions of higher pressure, the acidity of solution is improved, entered
And promoting shitosan to form stable solution under elevated pressure conditions, it is ensured that shitosan aqua dressing has normal physical and chemical states.
The high-pressure bottle is high pressure vessel or high-pressure container, and the high pressure vessel or high-pressure container are carried
Nozzle.
Used in the chitosan aqueous solution of preparation is incorporated with the high-pressure-resistant vessel bottle of nozzle by the present invention, on the one hand conveniently take
Band is used;On the other hand, container bottle is rocked by vibration during use, the carbon dioxide in solution is discharged, Jing sprays
After mouth sprays, the quick loss of carbon dioxide in shitosan aqua dressing is dissolved in shitosan therein and precipitates shape immediately
Into gel mould.
As a result of above-mentioned technical proposal, a kind of Advantageous effect of spary coating type shitosan aqua wound dressing of the invention
It is really:
1 adopt arbon dioxide solution for shitosan solvent, it is to avoid using sour agent residual in the chitosan film for being formed
Potential hazard to health, and the chitosan film for being formed has preferable resistance to water, gas permeability and pliability, is conducive to
Accelerate the healing of wound.
2, using the high-pressure-resistant vessel Bottle & Can dress shitosan aqua wound dressing for having nozzle, are on the one hand easy to carry.The opposing party
Face, before use, first vibration is rocked, and then high pressure extrusion sprays to wound again, forms chitosan film immediately, prevents shitosan molten
Scattering for liquid, it is easy to use.
Description of the drawings
Fig. 1:The dissolving situation of shitosan before and after carbon dioxide is passed through in embodiment 1, before left figure is for logical carbon dioxide, right figure
To be passed through enough carbon dioxide;
Fig. 2:The state diagram of chitosan gel rubber body in embodiment 1 and comparative example 1, left is 1 chitosan gel rubber of comparative example, and the right side is
1 chitosan gel rubber of embodiment;
Fig. 3:The petrographic microscope figure of different solution temperature shitosan dissolvings in embodiment 3;
Fig. 4:The petrographic microscope figure of different solution presasure shitosan dissolvings in embodiment 4;
Fig. 5:The infared spectrum that shitosan aqua wound dressing spraying film forming is obtained in embodiment 5;
Fig. 6:The outside drawing of the shitosan aqua wound dressing that embodiment 5 is obtained;
Specific embodiment
Make further in detail with reference to a kind of spary coating type shitosan aqua wound dressing of the specific embodiment to the present invention
Description:
Embodiment 1
The chitosan gel rubber body of 1g amounts is weighed, the viscosity-average molecular weight (M η) for preparing the shitosan of chitosan gel rubber body is
100000, deacetylation is 95%, is dispersed in the distilled water of 100mL with homogenizer, and the turbid liquid of finely dispersed shitosan is obtained;
Shitosan turbid liquid is maintained at into 5 DEG C, then under certain pressure state, carbon dioxide is passed through, and is observed solution colour
Change, it can be found that chitosan gel rubber turbid solution being passed through with carbon dioxide, solution has muddiness to be changed into clear shape
State.Therefore, it is known that, under conditions of cryogenic high pressure, chitosan gel rubber body is soluble in carbon dioxide.
Using petrographic microscope (DYP-990 type petrographic microscopes, Shanghai Dian Ying optical instruments Co., Ltd) observation logical two
Shitosan dissolved form condition before and after carbonoxide consumption, multiplication factor are 400 times, as a result see Fig. 1, it is seen which is being passed through enough titanium dioxides
The dissolving of shitosan can be promoted after carbon.
Embodiment 2
Shitosan is made into water gel, is then dispersed in distilled water, is continually fed under the conditions of high pressure low temperature
Carbon dioxide, obtains chitosan solution, then irradiated sterilizing, it is canned, obtain spary coating type shitosan aqua wound dressing, shell
Glycan aqua wound dressing is stored in high pressure vessel, and spary coating type shitosan aqua wound dressing is by shitosan, glycerine, dioxy
Change carbon and distillation aqueous systems composition, the weight/mass percentage composition of each component is respectively:Shitosan 4%, glycerine 2%, carbon dioxide
20%, distilled water 74%, wherein, select deacetylation=90% of shitosan, viscosity-average molecular weight (M η) to be respectively:10000,
50000,100000,170000.
The outward appearance of the spary coating type shitosan aqua wound dressing prepared to the shitosan of different viscosity-average molecular weights is taken pictures,
See Fig. 2, it is seen then that as the dissolubility of the increase spary coating type aqua of viscosity-average molecular weight is deteriorated, but when viscosity-average molecular weight is relatively low,
The viscosity of solution is poor, not easy-formation after spraying, therefore, viscosity-average molecular weight (M η) is in 50000-100000 as can be seen from Figure 2
When it is ideal
Embodiment 3
Shitosan is made into water gel, is then dispersed in distilled water, is continually fed under the conditions of high pressure low temperature
Carbon dioxide, obtains chitosan solution, then irradiated sterilizing, it is canned, obtain spary coating type shitosan aqua wound dressing, shell
Glycan aqua wound dressing is stored in high pressure vessel, and spary coating type shitosan aqua wound dressing is by shitosan, glycerine, dioxy
Change carbon and distillation aqueous systems composition, the weight/mass percentage composition of each component is respectively:Shitosan 4%, glycerine 2%, carbon dioxide
20%, distilled water 74%, wherein, viscosity-average molecular weight (M η) is:50000, select the deacetylation (DD) of shitosan to be respectively
75%, 90%, 95%.
The outward appearance of the spary coating type shitosan aqua wound dressing prepared to the shitosan for selecting different deacetylations is entered
Row is taken pictures, and sees Fig. 3, it is known that, the deacetylation of shitosan is higher, and the dissolubility of shitosan is better, when deacetylation is 75%
Dissolubility it is poor, most of shitosan is undissolved, it is contemplated that used as medical dressing, it is to avoid exist in dressing undissolved shell gather
Sugared particle, selects the deacetylation of shitosan to be more than 90%.
Embodiment 4
Shitosan is made into water gel, is then dispersed in distilled water, is continually fed under the conditions of high pressure low temperature
Carbon dioxide, obtains chitosan solution, then irradiated sterilizing, it is canned, obtain spary coating type shitosan aqua wound dressing, shell
Glycan aqua wound dressing is stored in high pressure vessel, and spary coating type shitosan aqua wound dressing is by shitosan, glycerine, dioxy
Change carbon and distillation aqueous systems composition, the weight/mass percentage composition of each component is respectively:Shitosan 3%, glycerine 2%, a certain amount of dioxy
Change carbon, distilled water supplements surplus, wherein, select the deacetylation of shitosan to be respectively 95%, viscosity-average molecular weight (M η) is:
50000, the consumption of carbon dioxide is 0%, 10%, 25%.
It is different using petrographic microscope (DYP-990 type petrographic microscopes, Shanghai Dian Ying optical instruments Co., Ltd) observation
The dissolved state of the spary coating type shitosan aqua wound dressing of carbon dioxide usage amount, multiplication factor are 400 times, as a result see Fig. 4, can
See which dissolves best in the case where carbon dioxide usage amount is 25%, it is contemplated that carbon dioxide usage amount can excessively cause high pressure
Container pressure is excessive and cause danger, select carbon dioxide consumption be 20-30%.
Embodiment 5
Shitosan is made into water gel, is then dispersed in distilled water, is continually fed under the conditions of high pressure low temperature
Carbon dioxide, obtains chitosan solution, then irradiated sterilizing, it is canned, obtain spary coating type shitosan aqua wound dressing, shell
Glycan aqua wound dressing is stored in high pressure vessel, and spary coating type shitosan aqua wound dressing is by shitosan, glycerine, dioxy
Change carbon and distillation aqueous systems composition, the weight/mass percentage composition of each component is respectively:Shitosan 3%, glycerine 2%, carbon dioxide
25%, distilled water 75%, wherein, select the deacetylation of shitosan to be respectively 95%, viscosity-average molecular weight (M η) is:50000.
The spary coating type shitosan aqua dressing for obtaining is the transparency liquid with certain viscosity, and its outward appearance is shown in Fig. 5.
The shitosan aqua wound dressing spraying film forming prepared in Example 5, is carried out to film after film is dried red
External spectrum is tested, referring to infrared spectrum Fig. 6, it can be seen that there is no the functional group of carboxyl from collection of illustrative plates, and in 1580 wave numbers
The residual of no acid in the crest of N-H flexural vibrations, therefore shitosan aqua wound dressing can be seen with 1658 wave numbers
Stay, secondary injury will not be produced to wound because of acid is remained in dressing in use.
Claims (8)
1. a kind of spary coating type shitosan aqua wound dressing, it is characterised in that:The shitosan aqua wound dressing is stored in height
In pressure vessel, spary coating type aqua wound dressing is made up of shitosan, glycerine, carbon dioxide and distillation aqueous systems, each component
Weight/mass percentage composition be respectively:
2. a kind of spary coating type shitosan aqua wound dressing as claimed in claim 1, it is characterised in that:Described shitosan
Viscosity-average molecular weight is 50000~100000, deacetylation >=90%.
3. a kind of spary coating type shitosan aqua wound dressing as claimed in claim 1, it is characterised in that:Described spraying shell
Glycan aqua wound dressing is to be dissolved in arbon dioxide solution to prepare by aquagel.
4. a kind of spary coating type shitosan aqua wound dressing as described in any one of claim 1-3, it is characterised in that:The height
The pressure of pressure vessel is 0.1MPa-0.5MPa.
5. a kind of spary coating type shitosan aqua wound dressing as described in any one of claim 1-3, it is characterised in that:The spray
It is pellucidity to apply the wound dressing of shell glycan aqua.
6. a kind of spary coating type shitosan aqua wound dressing as described in any one of claim 1-3, it is characterised in that:The height
There is no any gas beyond removing carbon dioxide in pressure vessel.
7. a kind of spary coating type shitosan aqua wound dressing as described in any one of claim 1-3, it is characterised in that:The height
Pressure vessel is high pressure vessel or high-pressure container, and the high pressure vessel or high-pressure container carry nozzle.
8. a kind of preparation method of the spary coating type shitosan aqua wound dressing as described in any one of claim 1-6, its feature
It is:Shitosan is made into water gel, is then dispersed in distilled water, dioxy is continually fed under the conditions of high pressure low temperature
Change carbon gas, obtain chitosan solution, then irradiated sterilizing, it is canned, obtain spary coating type shitosan aqua wound dressing.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020084416A1 (en) * | 2018-10-27 | 2020-04-30 | Shilpa Medicare Limited | Spray compositions of chitosan for wound healing |
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CN1546176A (en) * | 2003-12-17 | 2004-11-17 | 苗九昌 | Stealth water-proof spray paste for wound |
CN102824308A (en) * | 2012-08-31 | 2012-12-19 | 广州润虹医药科技有限公司 | Chitosan antibacterial filming sprayer and preparation method |
CN106170292A (en) * | 2014-02-04 | 2016-11-30 | 金珂生物医疗公司 | Chitosan material from carbon acid solution |
-
2016
- 2016-12-07 CN CN201611115634.7A patent/CN106512081A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1546176A (en) * | 2003-12-17 | 2004-11-17 | 苗九昌 | Stealth water-proof spray paste for wound |
CN102824308A (en) * | 2012-08-31 | 2012-12-19 | 广州润虹医药科技有限公司 | Chitosan antibacterial filming sprayer and preparation method |
CN106170292A (en) * | 2014-02-04 | 2016-11-30 | 金珂生物医疗公司 | Chitosan material from carbon acid solution |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2020084416A1 (en) * | 2018-10-27 | 2020-04-30 | Shilpa Medicare Limited | Spray compositions of chitosan for wound healing |
CN112955156A (en) * | 2018-10-27 | 2021-06-11 | 希尔帕医疗保健有限公司 | Chitosan spray composition for wound healing |
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Effective date of registration: 20190108 Address after: 264000 Xinzhuang Street 029, Zhifu District, Yantai City, Shandong Province Applicant after: Yantai Kang Kang Textile Technology Co., Ltd. Address before: 430073 No. 1 Textile Road, Hongshan District, Wuhan City, Hubei Province Applicant before: Wuhan Textile University |
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Application publication date: 20170322 |