CN106474523A - Preparation method based on the polyelectrolyte sponge wound dressing of carboxymethyl chitosan - Google Patents
Preparation method based on the polyelectrolyte sponge wound dressing of carboxymethyl chitosan Download PDFInfo
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Abstract
The invention belongs to biological medicine field of material preparation, is related to a kind of preparation method of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan.First appropriate carboxymethyl chitosan and anionic polyelectrolyte with biocompatibility or polyampholyte are dissolved in deionized water, are then injected in mould.By the pH value of the reduction polyelectrolyte mixtures aqueous solution, the protonated amino of carboxymethyl chitosan glycan molecule, interact to form compound and gradually gelation with anionic polyelectrolyte or polyampholyte by Coulomb force.Compound gel is freeze-dried, obtain spongy wound dressing, the polyelectrolyte sponge wound dressing of acquisition shows excellent hemostatic function and water suction performance of keeping humidity, can effective control wound produce diffusate, moisture is provided for drying type wound, accelerate the healing rate of wound, and easily remove from wound, while preparation process is simple, it is easy to industrialize.
Description
Technical field
The invention belongs to biological medicine field of material preparation, is related to a kind of polyelectrolyte based on carboxymethyl chitosan
The preparation method of sponge wound dressing.
Background technology
Modern medical service theoretical proof wound healing is cell and cell, cell and cellular matrix and is situated between with soluble
The continuous dynamic process of matter interphase interaction.The repair process of the surface of a wound and the nutrition of local organization, microenvironment, life
The interaction of many factors such as long factor content, microcirculation, hypoxia condition, infection is relevant, and medical dressing can
To play critical effect.As main theoretical basis of high-tech medical dressing, section of Britain in 1962
" the wet method therapy " that scholar has found thinks that epithelium is thin when the surface of wound is maintained in the microenvironment of a moistening
The migration of born of the same parents is significantly accelerated, and the healing rate of wound is faster than under dry environment.
Human body is bled profusely can cause haemorrhagic shock even dead, and no matter wartime live wire or pre hospital care are required for
A kind of quick, effectively can stop blooding, mitigate Hemostasis of the hemostasis to adverse effect that suffering limb blood circulation is caused.
Existing conventional Hemostasis and haemostatic medicament research and develop the wound with quick-acting haemostatic powder ability also far from requirement is met
Dressing is the research field that countries in the world are particularly that the military extremely pays close attention to.
Chitin be widely present Yu Haiyang crustacean shell, mollusk endoskeleton, insect wing, mushroom and
In alga cells wall, it is that tellurian reserves are only second to the natural polysaccharide of cellulose and second largest renewable resource.
Shitosan is the deacetylated product in strong base solution of chitin, is the band of only a large amount of presence in natural polysaccharide
Positive charge basic amine group polysaccharide, with special physics, chemistry and physiologically active and nontoxic, biodegradable,
Good biocompatibility, it is considered to be " the 6th vital principle of human body ".
Shitosan is readily dissolved in most of organic acids and inorganic acid, but insoluble in water, so as to limit answering for it
Use scope.Carboxymethyl chitosan is the product after shitosan carboxy methylation, according to the difference of carboxymethyl the position of substitution
Carboxymethylated product can be divided into O-CMC, N- carboxymethyl chitosan and N, O-CMC.
Carboxymethyl chitosan maintains good safe and nontoxic, the harmless, biocompatibility of shitosan and biological degradability,
While the introducing of carboxymethyl makes a kind of not only polyampholyte containing amino but also containing carboxyl, destroy
The original crystal structure of shitosan, improves its dissolving adaptability.Due to carboxyl and amino be all hydrophilic group because,
Carboxymethyl chitosan hydrophily is greatly improved, show stronger water suction moisture retention and film forming, thickening, flocculation,
The multifrequency natures such as chelating, gel and emulsification, are widely used in agricultural, environmental protection, medicine, cosmetics, food
Processing and other fields.
Carboxymethyl chitosan is widely studied in medical field as a kind of biomaterial, and research shows carboxylic first
Base enclosure glycan is shown compared with the more preferable antibiotic property of shitosan in the range of relatively wide substitution value.Due to carboxymethyl shell
Glycan can be connected with various bioactivators simultaneously containing active amino and carboxyl, it is possible to become a new generation
Gene and medicine targeted controlled-release carrier material.
In carboxymethyl chitosan glycan molecule, the pKa value of amino is about 6.5, when the pH value of solution is less than 6.0,
The amino of carboxymethyl chitosan glycan molecule is protonated.Therefore, when the pH value for adjusting solution is interval 3.0 to 6.0
When, the positively charged amino group of carboxymethyl chitosan glycan molecule can be with polyanion electrolyte or the poly- electrolysis of double property
Matter molecule simultaneously forms a kind of random compound by coulombic interaction.This compound is one kind
Nonequilibrium condition, As time goes on, by hydrogen bond, van der waals force, electric charge transfer and hydrophobic association
Other secondary such as active force interact and gradually form more stable compound.Compound using this polyelectrolyte
The three-dimensional net structure that thing is formed, can avoid in material preparation process using (such as：Glutaraldehyde etc.) have one
Determine the chemical cross-linking agent of toxicity, and can preferably retain the excellent performance of polyelectrolyte material itself, in biology
With important application prospect in field.
Content of the invention
Present invention aim at providing a kind of preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan
Method, the polyelectrolyte sponge wound dressing of acquisition show excellent hemostatic function and water suction performance of keeping humidity, solution
Certainly existing conventional Hemostasis and haemostatic medicament can not meet the problems such as requiring.
The technical scheme is that：
A kind of preparation method of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, prepares first and contains
Carboxymethyl chitosan and the solution of anionic polyelectrolyte or polyampholyte, the pH value for adjusting the solution make
Carboxymethyl chitosan is interacted to form compound by Coulomb force with anionic polyelectrolyte or polyampholyte
Gel, compound gel is freeze-dried to obtain spongy wound dressing.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, concrete steps are such as
Under：
1) mixing of the polyelectrolyte containing carboxymethyl chitosan and anionic polyelectrolyte or polyampholyte is prepared
The thing aqueous solution；
2) polyelectrolyte mixtures aqueous solution NaOH solution reconciles pH value between 7～9, is then injected into mould
In tool；
3) pH value for adjusting the polyelectrolyte mixtures aqueous solution is interval to 3.0～6.0, makes carboxymethyl chitosan sugar
The protonated amino of son, is interacted by Coulomb force with anionic polyelectrolyte or polyampholyte, is formed
Compound polyelectrolyte, and progressively gelation；
4) gel forms spongy wound dressing after precooling and vacuum freeze drying.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, step 1) poly-
In the electrolyte mixture aqueous solution, carboxymethyl chitosan molecular weight 10000～2000000, degree of substitution by carboxymethyl
For 28%～120%, the content of carboxymethyl chitosan is 0.1～8wt.% of the solution gross mass.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, step 1) poly-
In the electrolyte mixture aqueous solution, anionic polyelectrolyte or polyampholyte be with good biocompatibility
Containing-COO-、-SO3-、-O-CS2-、-O-PO3 2-Anionic group natural, semi-synthetic or synthesis organic
The content of macromolecular material, anionic polyelectrolyte or polyampholyte be the solution gross mass 0.2～
18wt.%.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, the moon of employing from
Sub- polyelectrolyte or polyampholyte are hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate,
Heparin, sodium alginate, xanthans, carboxymethylcellulose calcium, carragheen, pectin, gum arabic, thorn Chinese parasol tree
Glue, tragacanth gum, sodium lignin sulfonate, Carboxylic Derivates of Starch, polyacrylic acid, polymethylacrylic acid, polystyrene sulphur
Acid, polyvinyl sulfonic acid, polyvinylphosphonic acid, carboxymethyl chitosan, vinyl pyridine copolymer, nucleic acid,
One or more in protein.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, step 3) adjust
When the pH value of the section polyelectrolyte mixtures aqueous solution is to 3.0～6.0 interval, using in polyelectrolyte mixtures water
Proton release agent, polyelectrolyte mixtures aqueous solution immersion acid flux material or polyelectrolyte mixtures are added in solution
One or more in processing method in acid atmosphere of the aqueous solution.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, proton release agent
Using glucolactone, addition is 0.03～5wt.% of polyelectrolyte mixtures aqueous solution gross mass, place
The reason time is 30 minutes to 8 hours；Acid solution is the water of acid or alcohol solution, using inorganic acid or organic acid：
Hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, adipic acid, ethanedioic acid,
Malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA),
Valeric acid, caproic acid, capric acid, stearic acid, palmitic acid, acrylic acid, tartaric acid, malic acid, citric acid, anti-bad
Hematic acid, process time are 0.5 hour to 20 hours；
Acid atmosphere is using the inorganic acid for being easy to volatilize or organic acid：Hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid,
Ethanedioic acid, process time are 20 minutes to 18 hours.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, step 4) solidifying
Glue precooling temperature is -10 DEG C～-100 DEG C, and the precooling time is 4～50 hours.
The preparation method of the described polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, step 4) true
Below 30 handkerchiefs, vacuum drying time is 6～80 hours to vacuum freecing-dry process vacuum.
Advantages of the present invention and beneficial effect are：
1st, the characteristic that the present invention can be dissolved using carboxymethyl chitosan in neutral water, prepares containing carboxymethyl shell
The polyelectrolyte mixtures aqueous solution of glycan and anionic polyelectrolyte or polyampholyte.Molten by adjusting this
The pH value of liquid makes the protonated amino of carboxymethyl chitosan glycan molecule and the anion in lotus, with solution that becomes positively charged
Polyelectrolyte or polyampholyte interact to form compound gel by Coulomb force, and compound gel is through cold
Freeze and be dried to obtain spongy wound dressing.
2nd, the three-dimensional net structure that the present invention is formed using this compound polyelectrolyte, it is to avoid use (such as：
Glutaraldehyde etc.) there is the chemical cross-linking agent of certain toxicity, and can preferably retain the poly- electrolysis such as carboxymethyl chitosan
The excellent performance of material itself, shows clear advantage：With biocidal property and excellent hemostatic function；Inhale
Liquid energy power is strong, can quickly absorb the moisture in blood, Platelet Concentrate and clotting factor；Glue after water swelling
The surface of a wound is invested, blocks the capillary of surface of a wound rupture；Water gel is formed in the surface of a wound after hemostasis, be that wound is provided
Good wet environment, wound healing；Non-stimulated to wound, possess good biocompatibility and biology
Degradability；Preparation process is simple, it is easy to industrialize.
Description of the drawings
Fig. 1. carboxymethyl chitosan polyelectrolyte sponge wound dressing photo.
Specific embodiment
In a specific embodiment, system of the present invention based on the polyelectrolyte sponge wound dressing of carboxymethyl chitosan
Appropriate carboxymethyl chitosan and anionic polyelectrolyte with biocompatibility or both sexes are gathered by Preparation Method first
Electrolyte is dissolved in deionized water, is then injected in mould.By reducing the pH of the polyelectrolyte mixtures aqueous solution
Value, makes the protonated amino of carboxymethyl chitosan glycan molecule, and logical with anionic polyelectrolyte or polyampholyte
Cross Coulomb force to interact to form compound and gradually gelation.Compound polyelectrolyte gel is freeze-dried,
Obtain spongy wound dressing.Which concretely comprises the following steps：
1) mixing of the polyelectrolyte containing carboxymethyl chitosan and anionic polyelectrolyte or polyampholyte is prepared
The thing aqueous solution.Anionic polyelectrolyte or polyampholyte be with good biocompatibility containing-COO-、
-SO3-、-O-CS2-、-O-PO3 2-Deng the natural, semi-synthetic of anionic group or the high-molecular organic material of synthesis,
Such as：Hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin, sodium alginate, xanthan
Glue, carragheen, pectin, gum arabic, Karaya Gum, tragacanth gum (tragacanth Gum tragacanth),
Carboxymethylcellulose calcium, sodium lignin sulfonate, Carboxylic Derivates of Starch, polyacrylic acid, polymethylacrylic acid, polystyrene
Sulfonic acid, polyvinyl sulfonic acid, polyvinylphosphonic acid, carboxymethyl chitosan, vinyl pyridine copolymer, nucleic acid,
One or more in protein etc.；
2) in polyelectrolyte mixtures aqueous solution injection mould；
3) using addition proton release agent, the polyelectrolyte mixtures aqueous solution in the polyelectrolyte mixtures aqueous solution
In immersion acid flux material or the polyelectrolyte mixtures aqueous solution such as processes in acid atmosphere at the one kind or two in method
More than kind, the pH value for adjusting the polyelectrolyte mixtures aqueous solution is interval to 3.0～6.0, makes carboxymethyl chitosan
The amino of molecule is protonated, and is interacted by Coulomb force with anionic polyelectrolyte or polyampholyte,
Form compound polyelectrolyte, and progressively gelation；
4) compound polyelectrolyte gel forms spongy wound dressing after precooling and vacuum freeze drying.
For making technical scheme and advantage clearer, retouched below in conjunction with specific embodiment in detail
State.
Embodiment 1
8 grams of carboxymethyl chitosans, 13 grams of Sodium Polyacrylates and 1g glucolactones are molten in 1 liter of deionized water
Solution, is then injected in 10cm × 100cm × 30cm rectangle glass mould.After 10 hours being incubated at 50 DEG C, molten
Liquid forms gel.Gel is freezed 24 hours at -18 DEG C.It is vacuum dried under 5 handkerchief vacuums in vacuum drying chamber
After 60 hours, spongy carboxymethyl chitosan polyelectrolyte wound dressing is obtained.As shown in figure 1, carboxymethyl shell
Glycan polyelectrolyte sponge wound dressing photo, the wound dressing of the present embodiment show excellent hemostatic function and
Moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type wound provide moisture, accelerate wound
The healing rate of mouth, and easily remove from wound.The external clotting index of the present embodiment is determined and is shown, body
Outer clotting index<44%；The haemostatic effect testing result of rabbit arteria auricularis Hemorrhage Model shows, bleeding stopping period<77
Second.
Embodiment 2
8 grams of carboxymethyl chitosans, 10 grams of hyaluronic acids and 1g glucolactones are dissolved in 1 liter of deionized water,
It is then injected in 10cm × 100cm × 30cm rectangle glass mould.After 10 hours being incubated at 50 DEG C, solution shape
Become gel.Gel is freezed 24 hours at -18 DEG C.In vacuum drying chamber, under 5 handkerchief vacuums, vacuum drying 60 is little
Shi Hou, obtains spongy carboxymethyl chitosan polyelectrolyte wound dressing.The wound dressing of the present embodiment shows
Excellent hemostatic function and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type wound
Moisture is provided, is accelerated the healing rate of wound, and easily removes from wound.The external blood coagulation of the present embodiment
Assessment of indices shows, external clotting index<50%；The haemostatic effect testing result table of rabbit arteria auricularis Hemorrhage Model
Bright, bleeding stopping period<120 seconds.
Embodiment 3
8 grams of carboxymethyl chitosans, 10 grams of hyaluronic acids and 3g glucolactones are dissolved in 1 liter of deionized water,
It is then injected in 10cm × 100cm × 30cm rectangle glass mould.After 10 hours being incubated at 50 DEG C, solution shape
Become gel.Gel is freezed 24 hours at -18 DEG C.In vacuum drying chamber, under 5 handkerchief vacuums, vacuum drying 60 is little
Shi Hou, obtains spongy carboxymethyl chitosan polyelectrolyte wound dressing.The wound dressing of the present embodiment shows
Excellent hemostatic function and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type wound
Moisture is provided, is accelerated the healing rate of wound, and easily removes from wound.The external blood coagulation of the present embodiment
Assessment of indices shows, external clotting index<52%；The haemostatic effect testing result table of rabbit arteria auricularis Hemorrhage Model
Bright, bleeding stopping period<125 seconds.
Embodiment 4
8 grams of carboxymethyl chitosans, 12 grams of gum arabics and 1g glucolactones are molten in 1 liter of deionized water
Solution, is then injected in 10cm × 100cm × 30cm rectangle glass mould.After 10 hours being incubated at 50 DEG C, molten
Liquid forms gel.Gel is freezed 24 hours at -18 DEG C.It is vacuum dried under 5 handkerchief vacuums in vacuum drying chamber
After 60 hours, spongy carboxymethyl chitosan polyelectrolyte wound dressing is obtained.The wound dressing table of the present embodiment
Reveal excellent hemostatic function and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type
Wound provides moisture, accelerates the healing rate of wound, and easily removes from wound.The present embodiment external
Clotting index is determined and is shown, external clotting index<60%；The haemostatic effect detection knot of rabbit arteria auricularis Hemorrhage Model
Really show, bleeding stopping period<150 seconds.
Embodiment 5
12 grams of carboxymethyl chitosans, 15 grams of sodium alginates and 3g glucolactones are molten in 1 liter of deionized water
Solution, is then injected in 10cm × 100cm × 30cm rectangle glass mould.After 10 hours being incubated at 50 DEG C, molten
Liquid forms gel.Gel is freezed 24 hours at -18 DEG C.It is vacuum dried under 5 handkerchief vacuums in vacuum drying chamber
After 60 hours, spongy carboxymethyl chitosan polyelectrolyte wound dressing is obtained.The wound dressing table of the present embodiment
Reveal excellent hemostatic function and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type
Wound provides moisture, accelerates the healing rate of wound, and easily removes from wound.The present embodiment external
Clotting index is determined and is shown, external clotting index<39%；The haemostatic effect detection knot of rabbit arteria auricularis Hemorrhage Model
Really show, bleeding stopping period<88 seconds.
Embodiment 6
12 grams of carboxymethyl chitosans, 18 grams of Carboxylic Derivates of Starchs and 1g glucolactones are molten in 1 liter of deionized water
Solution, is then injected in 10cm × 100cm × 30cm rectangle glass mould.After 10 hours being incubated at 50 DEG C, molten
Liquid forms gel.Gel is freezed 24 hours at -18 DEG C.It is vacuum dried under 5 handkerchief vacuums in vacuum drying chamber
After 60 hours, spongy carboxymethyl chitosan polyelectrolyte wound dressing is obtained.The wound dressing table of the present embodiment
Reveal excellent hemostatic function and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type
Wound provides moisture, accelerates the healing rate of wound, and easily removes from wound.The present embodiment external
Clotting index is determined and is shown, external clotting index<70%；The haemostatic effect detection knot of rabbit arteria auricularis Hemorrhage Model
Really show, bleeding stopping period<150 seconds.
Embodiment 7
8 grams of carboxymethyl chitosans, 14 grams of sodium carboxymethylcelluloses are dissolved in 1 liter of deionized water, use NaOH
Solution reconciles pH value between 7～8, is then injected in 10cm × 100cm × 30cm rectangle polytetrafluoro mould.
0.3ml concentrated hydrochloric acid is dissolved in 3 liters of deionized waters, and the polyelectrolyte mixtures being slowly injected in mould are water-soluble
Liquid surface.After processing 4 hours at room temperature, the polyelectrolyte mixtures aqueous solution forms gel.Take out hydrochloric acid molten
Liquid, gel are freezed 24 hours at -80 DEG C.After being vacuum dried 60 hours under 3 handkerchief vacuums in vacuum drying chamber,
Obtain spongy carboxymethyl chitosan polyelectrolyte wound dressing.The wound dressing of the present embodiment shows excellent
Hemostatic function and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type wound provide water
Point, accelerate the healing rate of wound, and easily remove from wound.The external clotting index of the present embodiment is surveyed
Surely show, external clotting index<58%；The haemostatic effect testing result of rabbit arteria auricularis Hemorrhage Model shows, only
The blood time<123 seconds.
Embodiment 8
8 grams of carboxymethyl chitosans, 13 grams of Sodium Polyacrylates are dissolved in 1 liter of deionized water, and polyelectrolyte mixes
Thing aqueous solution NaOH solution reconciles pH value between 7～8, is then injected into 10cm × 100cm × 30cm rectangular
In shape polytetrafluoro mould.Mould equipped with the polyelectrolyte mixtures aqueous solution is put in acetic acid atmosphere.At room temperature
After processing 8 hours, the polyelectrolyte mixtures aqueous solution forms gel.Gel is freezed 24 hours at -80 DEG C.?
After being vacuum dried 48 hours under 3 handkerchief vacuums in vacuum drying chamber, the poly- electrolysis of spongy carboxymethyl chitosan is obtained
Matter wound dressing.The wound dressing of the present embodiment shows excellent hemostatic function and moisture-absorption water-retention performance, can have
The diffusate that effect control wound is produced, is that drying type wound provides moisture, accelerates the healing rate of wound, and
Easily remove from wound,.The external clotting index of the present embodiment is determined and is shown, external clotting index<48%；
The haemostatic effect testing result of rabbit arteria auricularis Hemorrhage Model shows, bleeding stopping period<129 seconds.
Embodiment 9
8 grams of carboxymethyl chitosans are dissolved in 500mL distilled water.13 grams of Sodium Polyacrylates are dissolved in 400mL
In distilled water.5g glucolactone is dissolved in 100mL distilled water.Merge carboxymethyl chitosan, poly- third
Olefin(e) acid sodium and glucolactone solution, are injected in 10cm × 100cm × 30cm rectangle glass mould.50℃
After lower insulation 10 hours, solution forms gel.Gel is freezed 24 hours at -18 DEG C.5 in vacuum drying chamber
After being vacuum dried 60 hours under handkerchief vacuum, spongy carboxymethyl chitosan polyelectrolyte wound dressing is obtained.This
The wound dressing of embodiment shows excellent hemostatic function and moisture-absorption water-retention performance, can the generation of effective control wound
Diffusate, be that drying type wound provides moisture, accelerate the healing rate of wound, and easily move from wound
Remove.The external clotting index of the present embodiment is determined and is shown, external clotting index<50%；Rabbit arteria auricularis bleeding mould
The haemostatic effect testing result of type shows, bleeding stopping period<120 seconds.
Embodiment 10
12 grams of carboxymethyl chitosans, 10 grams of sodium carboxymethylcelluloses and 12 grams of sodium alginates are in 1 liter of deionized water
Middle dissolving, polyelectrolyte mixtures aqueous solution NaOH solution reconcile pH value between 7～8, are then injected into
In 10cm × 100cm × 30cm rectangle polytetrafluoro mould.Mould equipped with the polyelectrolyte mixtures aqueous solution is put
Enter in acetic acid atmosphere.After processing 8 hours at room temperature, the polyelectrolyte mixtures aqueous solution forms gel.Gel
Freeze 24 hours at -80 DEG C.After being vacuum dried 48 hours under 3 handkerchief vacuums in vacuum drying chamber, sea is obtained
Continuous shape carboxymethyl chitosan polyelectrolyte wound dressing.The wound dressing of the present embodiment shows excellent hemostasis work(
Can and moisture-absorption water-retention performance, can effective control wound produce diffusate, be drying type wound provide moisture, plus
The healing rate of fast wound, and easily remove from wound.The external clotting index of the present embodiment is determined and is shown,
External clotting index<55%；The haemostatic effect testing result of rabbit arteria auricularis Hemorrhage Model shows, bleeding stopping period
<140 seconds.
Claims (9)
1. a kind of preparation method of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan, it is characterised in that：
Prepare the solution containing carboxymethyl chitosan and anionic polyelectrolyte or polyampholyte first, adjust this molten
The pH value of liquid makes carboxymethyl chitosan with anionic polyelectrolyte or polyampholyte by Coulomb force phase interaction
With compound gel is formed, compound gel is freeze-dried to obtain spongy wound dressing.
2. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 1
Method, it is characterised in that comprise the following steps that：
1) mixing of the polyelectrolyte containing carboxymethyl chitosan and anionic polyelectrolyte or polyampholyte is prepared
The thing aqueous solution；
2) polyelectrolyte mixtures aqueous solution NaOH solution reconciles pH value between 7～9, is then injected into mould
In tool；
3) pH value for adjusting the polyelectrolyte mixtures aqueous solution is interval to 3.0～6.0, makes carboxymethyl chitosan sugar
The protonated amino of son, is interacted by Coulomb force with anionic polyelectrolyte or polyampholyte, is formed
Compound polyelectrolyte, and progressively gelation；
4) gel forms spongy wound dressing after precooling and vacuum freeze drying.
3. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 2
Method, it is characterised in that step 1) in the polyelectrolyte mixtures aqueous solution, carboxymethyl chitosan molecular weight exists
10000～2000000, degree of substitution by carboxymethyl is 28%～120%, and the content of carboxymethyl chitosan is the solution
0.1～8wt.% of gross mass.
4. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 2
Method, it is characterised in that step 1) in the polyelectrolyte mixtures aqueous solution, anionic polyelectrolyte or both sexes
Polyelectrolyte be with good biocompatibility containing-COO-、-SO3-、-O-CS2-、-O-PO3 2-Anion base
The high-molecular organic material of the natural, semi-synthetic or synthesis of group, anionic polyelectrolyte or polyampholyte
Content is the 0.2～18wt.% of solution gross mass.
5. the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 2 or 4
Preparation method, it is characterised in that the anionic polyelectrolyte of employing or polyampholyte are hyaluronic acid, sulphur
Aching and limp ossein, dermatan sulfate, keratan sulfate, heparin, sodium alginate, xanthans, carboxymethylcellulose calcium,
Carragheen, pectin, gum arabic, Karaya Gum, tragacanth gum, sodium lignin sulfonate, Carboxylic Derivates of Starch, poly-
Acrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, polyvinylphosphonic acid, carboxymethyl chitosan
One or more in sugar, vinyl pyridine copolymer, nucleic acid, protein.
6. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 2
Method, it is characterised in that step 3) pH value of the polyelectrolyte mixtures aqueous solution is adjusted to 3.0～6.0 intervals
When, using addition proton release agent, the water-soluble immersion of polyelectrolyte mixtures in the polyelectrolyte mixtures aqueous solution
Enter acid flux material or the polyelectrolyte mixtures aqueous solution in processing method in acid atmosphere one or two with
On.
7. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 6
Method, it is characterised in that
Proton release agent adopts glucolactone, and addition is polyelectrolyte mixtures aqueous solution gross mass
0.03～5wt.%, process time are 30 minutes to 8 hours；
Acid solution is the water of acid or alcohol solution, using inorganic acid or organic acid：Hydrochloric acid, sulfuric acid, phosphoric acid,
Nitric acid, formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, adipic acid, ethanedioic acid, malonic acid, succinic acid, horse
Come sour, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA), valeric acid, caproic acid, capric acid,
Stearic acid, palmitic acid, acrylic acid, tartaric acid, malic acid, citric acid, ascorbic acid, process time are 0.5
Hour was to 20 hours；
Acid atmosphere is using the inorganic acid for being easy to volatilize or organic acid：Hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid,
Ethanedioic acid, process time are 20 minutes to 18 hours.
8. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 2
Method, it is characterised in that step 4) gel precooling temperature be -10 DEG C～-100 DEG C, the precooling time be 4～
50 hours.
9. the preparation of the polyelectrolyte sponge wound dressing based on carboxymethyl chitosan according to claim 2
Method, it is characterised in that step 4) vacuum freeze drying process vacuum below 30 handkerchiefs, during vacuum drying
Between be 6～80 hours.
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| CN107854722A (en) * | 2017-10-31 | 2018-03-30 | 温州医科大学附属第二医院、温州医科大学附属育英儿童医院 | A kind of liquid dressing and its application method for wound repair of two-component |
| CN108102150A (en) * | 2017-12-18 | 2018-06-01 | 北京理工大学 | A kind of method for building the polyelectrolyte composite material based on chitosan |
| CN109966540A (en) * | 2019-04-04 | 2019-07-05 | 武汉大学 | A kind of preparation method and application of nano-chitosan compound calcium alginate medical dressing |
| CN111388755A (en) * | 2020-03-20 | 2020-07-10 | 东华大学 | Injectable hyaluronic acid/chitosan hydrogel and preparation method thereof |
| CN111671968A (en) * | 2020-06-28 | 2020-09-18 | 瑞希(重庆)生物科技有限公司 | Chitosan/carrageenan hemostatic dressing and preparation method thereof |
| CN113174084A (en) * | 2021-04-07 | 2021-07-27 | 深圳市通产丽星科技集团有限公司 | Preparation method of polyurethane foam composite material |
| CN114349983A (en) * | 2022-01-10 | 2022-04-15 | 深圳市勇粒生物科技有限公司 | Anti-inflammatory and bactericidal amino acid hydrogel and preparation method and application thereof |
| CN115212343A (en) * | 2022-05-19 | 2022-10-21 | 季华实验室 | Blood vessel intervention drug-loaded gel embolic agent and preparation method thereof |
| CN116144082A (en) * | 2023-01-06 | 2023-05-23 | 科笛生物医药(无锡)有限公司 | Sodium hyaluronate and chitosan composite gel and preparation method and application thereof |
| CN116370697A (en) * | 2023-05-24 | 2023-07-04 | 季华实验室 | Gel sponge material and preparation method and application method thereof |
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| CN107854722A (en) * | 2017-10-31 | 2018-03-30 | 温州医科大学附属第二医院、温州医科大学附属育英儿童医院 | A kind of liquid dressing and its application method for wound repair of two-component |
| CN108102150A (en) * | 2017-12-18 | 2018-06-01 | 北京理工大学 | A kind of method for building the polyelectrolyte composite material based on chitosan |
| CN108102150B (en) * | 2017-12-18 | 2020-04-14 | 北京理工大学 | Method for constructing polyelectrolyte composite material based on chitosan |
| CN109966540A (en) * | 2019-04-04 | 2019-07-05 | 武汉大学 | A kind of preparation method and application of nano-chitosan compound calcium alginate medical dressing |
| CN111388755A (en) * | 2020-03-20 | 2020-07-10 | 东华大学 | Injectable hyaluronic acid/chitosan hydrogel and preparation method thereof |
| CN111671968A (en) * | 2020-06-28 | 2020-09-18 | 瑞希(重庆)生物科技有限公司 | Chitosan/carrageenan hemostatic dressing and preparation method thereof |
| CN113174084A (en) * | 2021-04-07 | 2021-07-27 | 深圳市通产丽星科技集团有限公司 | Preparation method of polyurethane foam composite material |
| CN114349983A (en) * | 2022-01-10 | 2022-04-15 | 深圳市勇粒生物科技有限公司 | Anti-inflammatory and bactericidal amino acid hydrogel and preparation method and application thereof |
| CN115212343A (en) * | 2022-05-19 | 2022-10-21 | 季华实验室 | Blood vessel intervention drug-loaded gel embolic agent and preparation method thereof |
| CN116144082A (en) * | 2023-01-06 | 2023-05-23 | 科笛生物医药(无锡)有限公司 | Sodium hyaluronate and chitosan composite gel and preparation method and application thereof |
| CN116370697A (en) * | 2023-05-24 | 2023-07-04 | 季华实验室 | Gel sponge material and preparation method and application method thereof |
| CN116370697B (en) * | 2023-05-24 | 2024-07-16 | 季华实验室 | Gel sponge material and preparation method and application method thereof |
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