CN106334209A - Polydopamine modified chitosan hemostatic dressing - Google Patents

Polydopamine modified chitosan hemostatic dressing Download PDF

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Publication number
CN106334209A
CN106334209A CN201510393645.0A CN201510393645A CN106334209A CN 106334209 A CN106334209 A CN 106334209A CN 201510393645 A CN201510393645 A CN 201510393645A CN 106334209 A CN106334209 A CN 106334209A
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shitosan
bleeding
poly
dopamine
stopping dressing
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CN201510393645.0A
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周建军
周旋
张新硕
李林
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Beijing Normal University
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Beijing Normal University
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Abstract

The invention discloses a polydopamine modified chitosan hemostatic dressing, which comprises: (a) a porous interpenetrating network formed by chitosan and polydopamine; and (b) at least one calcium salt. The invention also discloses a preparation method of the polydopamine modified chitosan hemostatic dressing. The polydopamine modified chitosan hemostatic sponge prepared according to the method provided by the invention not only has good hemostatic effect, but also has good adhesion properties to organism tissues like skin and organs, etc.

Description

Poly-dopamine modified lithium shitosan bleeding-stopping dressing
Technical field
The invention belongs to medical surgical bleeding-stopping dressing technical field, it is related to one kind and there is fine tissue adherence Poly-dopamine modified lithium shitosan bleeding-stopping dressing of energy and preparation method thereof.
Background technology
Chitosan derivative, in chitin, is the natural macromolecule amylose that in nature, yield is only second to cellulose.Shell Polysaccharide has numerous physiologically actives, such as antibacterial, lipid-loweringing, hemostasis, promote more, antitumor, antioxidation, raising Immunity etc..Simultaneously as they are all derived from organism, nonirritant, nonantigenic immunity, tool There are good histocompatibility, and the bacteriolyze enzymatic degradation that can be widely present in animal body tissue, generate no Poison and the natural bioactive substances that can be fully absorbed by organism, therefore, medicine, biology, chemical industry, environment, All many-sides such as food show good application prospect.
As the raw material of wound dressing, chitin and chitosan because its have hemostasis, promote more, antiinflammatory, pain relieving, Reduce cicatrix, the excellent performance such as antibacterial, it has also become a focus of functional living being hemostatic material research. A kind of applied by the compounded spongy biological that shitosan, collagen and calcium alginate are made as disclosed in cn1167366 Material, has good biocompatibility, adhesiveness, wound healing promoting and hemostatic function.In cn1217706 In disclose a kind of sponge hemostatic material made with shitosan/chitin for raw material, there is good hemostasis and live Property and promotion organization repair biological activity and stronger adhesiveness.Cn1229148 discloses a kind of with The Antiadhesive film that water-soluble chitosan is prepared for primary raw material, has hemostasis, Conservative restoration and promotes wound to heal The effect closed.Disclose one kind shitosan and sodium alginate preparation hemostasis in cn100411690, apply wound The method of the porous material of mouth, the porous material of preparation has higher water absorption rate and shorter bleeding stopping period. Disclose one kind Human-like Collagen and biodegradable hemostasis sea prepared by shitosan in cn100415304 The method of continuous material.Disclose one kind and utilize polyacrylic acid, polyvinylpyrrolidone in cn101502667 Chitosan transparent hydrogel wound dressing prepared by ketone and shitosan, has the characteristics that anti-inflammation hemostasia, water absorption are high. Cn101897990 discloses a kind of using the suppression being made up of shitosan, acidic polysaccharose and Radix Notoginseng total arasaponinss Cicatrix processed and the compositionss promoting wound healing.Shitosan has good anastalsis, but and wound Adhesiveness still have much room for improvement.
Mussel is that one kind is prevalent in bank and coastal waters, the especially Crustacean in cold water marine site.Their energy Enough pass through to secrete superpower mucus by oneself be attached on the reef of seashore or steamer bottom, just at last in ripple The surging billow of great waves remains to be adhere tightly to steamer ground under washing away.Moreover, they can be by oneself pole It is attached on metal securely, glass, on polymer and the first-class any material of mineral surfaces, or even can be from Oneself securely adheres to sequestering power on the extremely difficult teflon surface sticked, can be with protein isopolarity polymer Form very strong hydrogen bond.The superpower waterproof of mussel is sticked very tempting with omnipotent Adhesion property.Research finds, Mussel is by a kind of very special mucus of byssus glandular secretion, and this mucus solidify to form glutinous immediately after meeting sea water Attached disk, adheres closely to ground.The main component of mucus is mussel adhesion protein, its unique one It is structurally characterized in that aminoacid this containing dopamine (dihydroxyphenylalanine).Catechol group in dopamine (also known as catechol) has the multi-functional and affine multiformity of chemistry, is the key of the superpower Adhesion property of mussel.For Raising chitosan-based styptic sponge materials microstructure adhesiveness, discloses a kind of logical in cn104013990 Cross shitosan and dopamine or there is the compound of catechol based structures react, preparation has catechol structure Chitosan material, it is said that the sthptic sponge made has good tissue affinity.
Content of the invention
It is an object of the invention to provide a kind of poly-dopamine modified lithium shitosan bleeding-stopping dressing.
It is a further object of the present invention to provide a kind of preparation side preparing poly-dopamine modified lithium shitosan bleeding-stopping dressing Method.
Specific embodiment
The invention provides a kind of poly-dopamine modified lithium shitosan bleeding-stopping dressing, it is vesicular texture, comprising:
A stephanoporate interpenetrating network that () shitosan is formed with poly-dopamine;
(b) at least one calcium salt.
Shitosan in described shitosan bleeding-stopping dressing both can be non-modified shitosan or process Modified chitosan salt, the such as acetate of shitosan, hydrochlorate, lactate etc., can also be through other The shitosan of chemical modification, such as carboxyetbyl chitosan etc..The deacetylation of described shitosan is 50-99%, Excellent for 70-90%.The weight average molecular weight of described shitosan is 10,000~150,000, and optimum is 1.5 ten thousand~80,000. Weight content in bleeding-stopping dressing for the shitosan is 85-98%.
Described poly-dopamine for dopamine hydrochlorate by adjust ph value to alkalescence after autohemagglutination and obtain.Poly- many Weight content in bleeding-stopping dressing for the bar amine is 2-20%.
Described calcium salt be with inorganic or organic acid by calcium hydroxide and rear generation salt, both can be inorganic salt such as Calcium chloride etc. or acylate such as calcium acetate, calcium lactate, calcium salicylate, gallic acid calcium, coffee Coffee acid calcium etc..Weight content in bleeding-stopping dressing for the calcium salt is 5-10%.
In order to improve pliability and the comfort level of shitosan bleeding-stopping dressing, can also contain in shitosan bleeding-stopping dressing There is plasticizer.Weight content in bleeding-stopping dressing for the plasticizer is 0-10%.Described plasticizer be glycerol, Polyethylene glycol 200, PEG400, propylene glycol etc..
Another aspect of the present invention provides the preparation method of poly-dopamine modified lithium shitosan bleeding-stopping dressing, walks including following Rapid: a. adds shitosan in appropriate water, it is configured to solution or the suspension of mass concentration 0.5-5%, make Shitosan is completely dissolved or fully swelling;B. dopamine hydrochloride is added fully to dissolve toward in chitosan solution; C. adjusted with calcium hydroxide and contain the chitosan solution of dopamine hydrochloride or the ph value of suspension to alkalescence, continue Stirring makes dopamine autohemagglutination form poly-dopamine;D. with acid, ph value is adjusted to neutrality or acidity, stirring It is completely dissolved to shitosan;E. add plasticizer toward in solution, after stirring, lyophilization, is gathered The modified chitosan sponge of dopamine;F. by chitosan sponge in 70-90 DEG C of hot pressing, obtaining density is 0.15-0.5g/cm3Shitosan bleeding-stopping dressing.Stop by the shitosan of the poly-dopamine modified lithium of the inventive method preparation Blood dressing not only has good anastalsis, bio-tissue such as skin, organ etc. is had very well simultaneously Adhesion property.
Method of testing
Anthemorrhagic performance: take the shitosan bleeding-stopping dressing of 1cm × 1cm to be placed in vial, instill 120 μ l rabbit whole bloods (anticoagulant containing 1: 6), adds 10ml water in 37 DEG C of effect 30s tailing edge bottle walls, does not send out after 10min The raw erythrocytolysis condensing, in water, measure wavelength X with uv absorption540nmThe absorbance at place is molten to characterize In Xie Shui, the amount of hematochrome is to carry out the evaluation of anthemorrhagic performance.Absorbance shows more greatly to be dissolved in water Erythrocyte is more, and anthemorrhagic performance is poorer.
Adhesion property: the adhesion property of shitosan bleeding-stopping dressing is entered with instron3366 electronic universal cupping machine Row measurement.Shitosan bleeding-stopping dressing is pasted onto on stationary fixture, fresh Radix Polygalae Crotalarioidis are cut into 1cm2Square It is fixed on movable clamp.Movable clamp is pressed in 0.1n pressurize on stationary fixture with the speed of 0.1mm/min After 3min, left with the speed of 0.1mm/min, characterize shitosan hemostasis with maximum adhesion when disengaging and apply The adhesion property to tissue for the material.
Embodiment 1
The shitosan that deacetylation 85%, weight average molecular weight are 30,000 adds in ultra-pure water, stirs to complete After swelling, form the suspension that mass concentration is 2%, add the dopamine with respect to ultrapure water quality 0.2% Hydrochlorate, instills the calcium hydroxide aqueous solution of appropriate saturation after being completely dissolved, solution is adjusted to alkalescence, Stir and be polymerized formation dark brown solution completely to dopamine.It is neutralized with hydrochloric acid to neutrality, add toward in solution With respect to the glacial acetic acid of ultrapure water quality 2%, stir and be completely dissolved to shitosan.It is subsequently added with respect to ultrapure The glycerol of water quality 0.5%, stirs.Will be dry to the poly-dopamine preparing chitosan solution deaeration, freezing After dry, obtain the chitosan sponge of poly-dopamine modified lithium.By sponge in 80 DEG C of hot pressing, obtain poly-dopamine and change The shitosan bleeding-stopping dressing of property, its adhesion property is shown in Table 1.
Embodiment 2
The chitosan lactate that deacetylation 90%, weight average molecular weight are 1.5 ten thousand is dissolved in ultra-pure water, stirring To after be completely dissolved, form the solution that mass concentration is 3%.Add with respect to ultrapure water quality toward in solution 0.4% dopamine hydrochloride, adds the calcium hydroxide aqueous solution of appropriate saturation, solution is adjusted after being completely dissolved Save to alkalescence, stir and be polymerized formation dark brown solution completely to dopamine.Hydrochloric acid is added to make toward in solution molten The ph value of liquid is adjusted to neutrality, stirs and is completely dissolved to shitosan, is subsequently added with respect to ultrapure water quality 0.5% peg200, stirs.By the poly-dopamine preparing chitosan lactate solution deaeration, freezing After drying, obtain the chitosan lactate sponge of poly-dopamine modified lithium.By sponge in 80 DEG C of hot pressing, gathered The modified chitosan lactate bleeding-stopping dressing of dopamine, its adhesion property is shown in Table 1.
Embodiment 3
The shitosan that deacetylation 80%, weight average molecular weight are 50,000 adds in ultra-pure water, stirs to complete After swelling, form the suspension that mass concentration is 1.5%.Add with respect to ultrapure water quality 0.5% dopamine Hydrochlorate, instills the calcium hydroxide aqueous solution of appropriate saturation after dissolving, solution is adjusted to alkalescence, stirring It is polymerized formation dark brown solution to dopamine completely.Add hydrochloric acid to adjust to neutrality toward in solution, add phase For the acetic acid of ultrapure water quality 3%, heating makes shitosan be completely dissolved, is subsequently added with respect to ultrapure water quality The glycerol of amount 1%, stirs.After the shitosan preparing poly-dopamine solution lyophilization, gathered The modified chitosan sponge of dopamine.Sponge is obtained the shitosan hemostasis of poly-dopamine modified lithium in 75 DEG C of hot pressing Dressing, its adhesion property is shown in Table 1.
Embodiment 4
Deacetylation 95%, weight average molecular weight are stirring in 20,000 carboxyetbyl chitosan addition ultra-pure water To after be completely dissolved, form the suspension that mass concentration is 1.5%.Add with respect to ultrapure water quality 0.5% Dopamine hydrochloride, instills the calcium hydroxide aqueous solution of appropriate saturation after dissolving, solution is adjusted to alkalescence, Stir and be polymerized formation dark brown solution completely to dopamine.Toward in solution, hydrochloric acid is adjusted to neutrality, adds phase For the caffeic acid of ultrapure water quality 3%, heating makes shitosan be completely dissolved, is subsequently added with respect to ultra-pure water The glycerol of quality 1%, stirs.After the shitosan preparing poly-dopamine solution lyophilization, obtain The chitosan sponge of poly-dopamine modified lithium.The shitosan that sponge is obtained poly-dopamine modified lithium in 75 DEG C of hot pressing stops Blood dressing, its adhesion property is shown in Table 1.
Reference examples 1
The shitosan that deacetylation 80%, weight average molecular weight are 50,000 adds in ultra-pure water, stirs to complete After swelling, add the glacial acetic acid with respect to ultrapure water quality 2%, so that shitosan is completely dissolved, be subsequently added phase For the glycerol of ultrapure water quality 0.5%, stir.After the chitosan solution preparing lyophilization, Obtain chitosan sponge.Sponge is obtained shitosan bleeding-stopping dressing in 75 DEG C of hot pressing, its adhesion property is shown in Table 1.
The adhesion property of table 1 shitosan bleeding-stopping dressing

Claims (7)

1. a kind of poly-dopamine modified lithium shitosan bleeding-stopping dressing, comprising:
(a) shitosan and poly-dopamine;
(b) at least one calcium salt.
2. poly-dopamine modified lithium shitosan bleeding-stopping dressing as claimed in claim 1, wherein shitosan is in bleeding-stopping dressing In content be 85-98 weight %;Content in bleeding-stopping dressing for the poly-dopamine is 2-20 weight %;Calcium Content in bleeding-stopping dressing for the salt is 5-10 weight %;Content in bleeding-stopping dressing for the plasticizer is 0-10 Weight %.
3. poly-dopamine modified lithium shitosan bleeding-stopping dressing as claimed in claim 1 or 2, wherein shitosan gather for shell Sugar and/or the derivant of shitosan, the such as acetate of shitosan, hydrochlorate, lactate, carboxymethyl chitosan Sugar, carboxyetbyl chitosan etc..
4. the poly-dopamine modified lithium shitosan bleeding-stopping dressing as described in any one in claim 1-3, wherein shell gather The deacetylation of sugar is 50-99%, and optimum is 70-90%.
5. the poly-dopamine modified lithium shitosan bleeding-stopping dressing as described in any one in claim 1-4, wherein shell gather The weight average molecular weight of sugar is 10,000~150,000, and optimum is 1.5 ten thousand~80,000.
6. poly-dopamine modified lithium shitosan bleeding-stopping dressing as claimed in claim 1 or 2, calcium salt therein is chlorination Calcium, calcium acetate, calcium lactate, calcium salicylate, gallic acid calcium, caffeic acid calcium etc..
7. a kind of side preparing poly-dopamine modified lithium shitosan bleeding-stopping dressing described in any one in claim 1-6 Method, comprises the steps: that a. adds shitosan in appropriate water, is configured to mass concentration 0.5-5% Solution or suspension, so that shitosan is completely dissolved or fully swelling;B. add many toward in chitosan solution Bar amine hydrochlorate fully dissolves;C. the chitosan solution or outstanding containing dopamine hydrochloride is adjusted with calcium hydroxide The ph value of supernatant liquid to alkalescence, continuously stirred make dopamine autohemagglutination formed poly-dopamine;D. with sour by ph Value is adjusted to neutrality or acidity, stirs and is completely dissolved to shitosan;E. add plasticizer toward in solution, After stirring, lyophilization, obtain the chitosan sponge of poly-dopamine modified lithium;F. by chitosan sponge In 70-90 DEG C of hot pressing, obtaining density is 0.15-0.5g/cm3Shitosan bleeding-stopping dressing.
CN201510393645.0A 2015-07-08 2015-07-08 Polydopamine modified chitosan hemostatic dressing Pending CN106334209A (en)

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Cited By (16)

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CN107375196A (en) * 2017-07-26 2017-11-24 暨南大学 A kind of natural polysaccharide composite aquogel carrier of phenolic group containing catechu and preparation method thereof
CN107998442A (en) * 2017-12-08 2018-05-08 大连理工大学 External application nano silicon dioxide/poly-dopamine adhesion type hemostatic material and preparation method thereof
CN108159508A (en) * 2018-01-03 2018-06-15 东南大学 A kind of preparation method of anti-adhesion medical hydrogel material
CN109701070A (en) * 2018-12-13 2019-05-03 青岛大学 A kind of antibacterial hybridized nanometer flower hemostatic material and preparation method thereof
CN110123523A (en) * 2019-04-16 2019-08-16 温州大学 A kind of near-infrared stress type plasma diffusing W,Mo antiseptic dressing, the method and dressing combination that promote release
CN110420344A (en) * 2019-07-16 2019-11-08 温州大学 A kind of wound dressing and the preparation method and application thereof
CN110420345A (en) * 2019-08-02 2019-11-08 北京化工大学常州先进材料研究院 High water absorption antibacterial anti hemorrhagic sponge
CN110684212A (en) * 2019-10-31 2020-01-14 东南大学 Preparation method of mussel-imitated underwater high-viscosity hydrogel
CN111905143A (en) * 2020-06-17 2020-11-10 西安交通大学 Multifunctional tissue adhesion crystal gel dressing and preparation method and application thereof
CN112480433A (en) * 2020-11-30 2021-03-12 东南大学成贤学院 Adhesive chitosan-alginate hydrogel and preparation and application methods thereof
CN112891625A (en) * 2021-02-01 2021-06-04 南方医科大学南方医院 Polydopamine secondary polymerization collagen sponge scaffold and preparation method and application thereof
CN113209365A (en) * 2021-05-31 2021-08-06 福州大学 Multifunctional closed hemostatic wound dressing and preparation method thereof
CN113398002A (en) * 2021-06-30 2021-09-17 绽妍生物科技有限公司 Desensitizing toothpaste containing modified chitosan and capable of repairing gingiva and preparation process of desensitizing toothpaste
CN113398310A (en) * 2021-06-28 2021-09-17 福建师范大学 Chitosan catechol hemostatic gauze and preparation method thereof
CN114213905A (en) * 2021-12-24 2022-03-22 李金彪 Dialysis harbor and dialysis harbor surface coating material and preparation method thereof
CN116102769A (en) * 2021-11-11 2023-05-12 武汉大学 Carboxymethyl chitin hemostatic sponge material, preparation method and application

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Cited By (23)

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CN107375196B (en) * 2017-07-26 2020-02-07 暨南大学 Catechol-based natural polysaccharide composite hydrogel carrier and preparation method thereof
CN107375196A (en) * 2017-07-26 2017-11-24 暨南大学 A kind of natural polysaccharide composite aquogel carrier of phenolic group containing catechu and preparation method thereof
CN107998442A (en) * 2017-12-08 2018-05-08 大连理工大学 External application nano silicon dioxide/poly-dopamine adhesion type hemostatic material and preparation method thereof
CN107998442B (en) * 2017-12-08 2019-11-26 大连理工大学 External application nano silica/poly-dopamine adhesion type hemostatic material and preparation method thereof
CN108159508A (en) * 2018-01-03 2018-06-15 东南大学 A kind of preparation method of anti-adhesion medical hydrogel material
CN109701070B (en) * 2018-12-13 2021-06-08 青岛大学 Antibacterial hybrid nanoflower hemostatic material and preparation method thereof
CN109701070A (en) * 2018-12-13 2019-05-03 青岛大学 A kind of antibacterial hybridized nanometer flower hemostatic material and preparation method thereof
CN110123523A (en) * 2019-04-16 2019-08-16 温州大学 A kind of near-infrared stress type plasma diffusing W,Mo antiseptic dressing, the method and dressing combination that promote release
CN110420344A (en) * 2019-07-16 2019-11-08 温州大学 A kind of wound dressing and the preparation method and application thereof
CN110420345A (en) * 2019-08-02 2019-11-08 北京化工大学常州先进材料研究院 High water absorption antibacterial anti hemorrhagic sponge
CN110684212A (en) * 2019-10-31 2020-01-14 东南大学 Preparation method of mussel-imitated underwater high-viscosity hydrogel
CN111905143A (en) * 2020-06-17 2020-11-10 西安交通大学 Multifunctional tissue adhesion crystal gel dressing and preparation method and application thereof
CN111905143B (en) * 2020-06-17 2021-09-07 西安交通大学 Multifunctional tissue adhesion crystal gel dressing and preparation method and application thereof
CN112480433A (en) * 2020-11-30 2021-03-12 东南大学成贤学院 Adhesive chitosan-alginate hydrogel and preparation and application methods thereof
CN112891625A (en) * 2021-02-01 2021-06-04 南方医科大学南方医院 Polydopamine secondary polymerization collagen sponge scaffold and preparation method and application thereof
CN113209365A (en) * 2021-05-31 2021-08-06 福州大学 Multifunctional closed hemostatic wound dressing and preparation method thereof
CN113209365B (en) * 2021-05-31 2022-04-01 福州大学 Multifunctional closed hemostatic wound dressing and preparation method thereof
CN113398310A (en) * 2021-06-28 2021-09-17 福建师范大学 Chitosan catechol hemostatic gauze and preparation method thereof
CN113398002A (en) * 2021-06-30 2021-09-17 绽妍生物科技有限公司 Desensitizing toothpaste containing modified chitosan and capable of repairing gingiva and preparation process of desensitizing toothpaste
CN113398002B (en) * 2021-06-30 2023-01-10 绽妍生物科技有限公司 Desensitizing toothpaste containing modified chitosan and capable of repairing gingiva and preparation process of desensitizing toothpaste
CN116102769A (en) * 2021-11-11 2023-05-12 武汉大学 Carboxymethyl chitin hemostatic sponge material, preparation method and application
CN116102769B (en) * 2021-11-11 2024-03-19 武汉大学 Carboxymethyl chitin hemostatic sponge material, preparation method and application
CN114213905A (en) * 2021-12-24 2022-03-22 李金彪 Dialysis harbor and dialysis harbor surface coating material and preparation method thereof

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Application publication date: 20170118