CN106519264B - Double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide - Google Patents
Double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide Download PDFInfo
- Publication number
- CN106519264B CN106519264B CN201610994581.4A CN201610994581A CN106519264B CN 106519264 B CN106519264 B CN 106519264B CN 201610994581 A CN201610994581 A CN 201610994581A CN 106519264 B CN106519264 B CN 106519264B
- Authority
- CN
- China
- Prior art keywords
- chemical
- network
- physical
- mixed solution
- double
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
- A61K47/38—Cellulose; Derivatives thereof
-
- 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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0031—Hydrogels or hydrocolloids
-
- 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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/08—Polysaccharides
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/042—Polysaccharides
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/145—Hydrogels or hydrocolloids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide.The chemical-physical/chemistry double-network hydrogel is formed with the second physical/chemical network through interaction of hydrogen bond by the first chemical network；First chemical network is formed by polyethyleneglycol derivative 1 and polyethyleneglycol derivative 2 through chemical reaction；The second physical/chemical network be it is following 1) or 2): 1) by the crosslinked formation of polysaccharide or derivatives thereof；2) it is interacted and is formed with crosslinking agent by polysaccharide or derivatives thereof.The present invention has potential application: Thermosensitive Material Used for Controlled Releasing of Medicine in following field with the good high-strength chemistry-physical/chemical double-network hydrogel of automatic recovery ability biocompatibility；Tissue engineering bracket；Medical sponge；Medical inner matter；The surface covering of medical inner matter.
Description
Technical field
The present invention relates to a kind of double-network hydrogels, and in particular to a kind of double-network hydrogel based on PEG and polysaccharide and
Preparation method and application.
Background technique
Hydrogel is a kind of soft substance that large quantity of moisture can be absorbed and have three-dimensional net structure.Hydrogel Yin Qigao inhales
Aqueous and good biocompatibility is thus widely used in the fields such as bio-medical, agricultural, industry, environmental protection.In life
The medical aspect of object, hydrogel have been applied to pharmaceutical carrier, cell carrier, dressing, facial mask and artificial cornea etc..However it is right
In the cartilage of load-bearing, for tendon and ligament class soft tissue, traditional hydrogel cannot be met the requirements.
In recent years, there is the dual network gel compared with high-mechanical property to have received widespread attention, and becomes in hydrogel and grinds
One of hot spot studied carefully.So-called double-network hydrogel (Double-Network Hydrogel) refers to that inside gel include two
Mutually interspersed network, one of them is the very high rigid polymer network of the degree of cross linking, and the other is the degree of cross linking is lower soft
Property polymer network, due to the low crosslinking degree of the second network make network have certain mobile performance, pass through polymer segment
Physics entwines sliding a little or the deformation of whole network and effectively absorbs energy to failure, in this way it is prevented that crackle it is further
Extension, to embody excellent mechanical property.
The most common dual network gel preparation generallys use two-stage polymerization method: first network monomer, crosslinking agent, dispersion are situated between
Matter, initiator are dissolved in the water, and by solution in a mold under strong ultraviolet radioactive, obtain the strong polyelectrolyte water-setting of high-crosslinking-degree
Glue.Then hydrogel is removed from the molds, it is pre- anti-is put into the second network containing the second network monomer, crosslinking agent, initiator
It answers in solution and is sufficiently swollen；Finally, light initiation polymerization, which forms the second network being loosely crosslinked, obtains double chemical network gels.This
Kind method is complicated, and the used time needs 2~5 days, and the gel being prepared having differences property due to the difference of each swellability can not
Guarantee its same mechanical property.Due to the complexity of operating procedure, it is difficult to construct hydrogel with complex shape.Not only such as
This, free radical polymerization generally involves toxic initiator and polyacrylamide materials, limits dual network gel and cures in biology
With the application of aspect.These disadvantages seriously limit double applications of the chemical network in bioengineering.
Chinese patent application (201410375076.2) discloses a kind of chitosan-based double-network hydrogel, which is
Dual network structure, wherein first network be chitosan graft hydrogel, the chitosan graft hydrogel by chitosan solution, draw
Hair agent, the first monomer and crosslinking agent carry out graft reaction and form, and the second network is interspersed in the inside of first network, the second network
For the hydrogel being polymerized under ultraviolet light by second comonomer, crosslinking agent and photoinitiator.The double-network hydrogel exists
Still it is related to multistep reaction in preparation process, the shape of various complexity cannot be prepared, and the introducing of radical polymerization credit union has
The substance of poison.
Summary of the invention
The object of the present invention is to provide a kind of double-network hydrogel and preparation method thereof based on PEG and polysaccharide, the present invention
The double-network hydrogel of offer has automatic recovery ability and biocompatibility is good.
Chemical-physical provided by the present invention/chemistry double-network hydrogel, by the first chemical network and the second physics/
Chemical network is formed through interaction of hydrogen bond；
First chemical network is formed by polyethyleneglycol derivative 1 and polyethyleneglycol derivative 2 through chemical reaction；
The second physical/chemical network be it is following 1) or 2):
1) by the crosslinked formation of polysaccharide or derivatives thereof；
2) it is interacted and is formed with crosslinking agent by polysaccharide or derivatives thereof.
In the chemical-physical/chemistry double-network hydrogel, the second physical/chemical network and first chemistry
Mass ratio between network can be 1:1~50, concretely 1:1~20,1:1~10,1:1~8,1:4 or 1:8.
In the chemical-physical/chemistry double-network hydrogel, the polyethyleneglycol derivative 1 and the polyethylene glycol spread out
Biology 2 is any in Formulas I, Formula II, formula III and formula IV:
In various, n is the number between 2~10000, concretely 21~56,21,23,43,45 or 56；
R1For ehter bond, acetyl group, ester bond, ammonia ester bond, amido bond or carbon atom number be 1~30 straight-chain, branched or
Cricoid alkylidene, preferably ehter bond, ester bond or amido bond；
R2For amino, carboxyl, succinimide ester, aldehyde radical, sulfydryl, alkenyl, alkynyl, acrylate-based, acrylamido,
It is any in azido group, epoxy group, maleic amide group, catechol group, phenolic hydroxyl group, cyclodextrin, adamantane and azobenzene
Kind, preferably amino, succinimide ester, sulfydryl, alkynyl or azido group；
The polyethyleneglycol derivative 1 and the polyethyleneglycol derivative 2 are through R2In any two groups to carry out chemistry anti-
First chemical network should be formed.
In the chemical-physical/chemistry double-network hydrogel, described polysaccharide or derivatives thereof can be agar, agarose, sea
Mosanom, cellulose, starch, hyaluronic acid or their derivative；
The agarose concretely conventional agarose, low electric osmose agarose, high-intensitive agarose, low melting-point agarose or
High electric osmose agarose, preferred high strength agarose；
The cellulose concretely ethyl cellulose, cellulose acetate, hydroxypropyl methylcellulose, cellulose propionic acid or adjacent benzene
Dioctyl phthalate cellulose acetate, preferably cellulose acetate.
In the chemical-physical/chemistry double-network hydrogel, 2) in, the interaction can be made for electrostatic interaction, crystallization
With, molecule aggtegation, ionization, hydrogen bond action, chain winding effect, free radical polymerization, amidation process or Schiff
Alkali reaction.
In the chemical-physical/chemistry double-network hydrogel, the crosslinking agent can be alkali, the anion of unit price, multivalence
At least one of anion, anionic metal, radical initiator or aldehyde compound, can be with the polysaccharide or its derivative
Object interaction.
The alkali can be organic base or inorganic base；
The organic base concretely triethylamine and/or ammonium hydroxide；
The inorganic base concretely sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, iron hydroxide, hydroxide
At least one of ferrous, Kocide SD and cuprous hydroxide；
The anion of the unit price can for chloride ion, fluorine ion, bromide ion, iodide ion, bicarbonate radical, bisulfite,
At least one of nitrate anion, nitrite anions, sulphur hydrogen radical, MnO4, hypochlorite, chlorate anions, metaphosphoric acid radical and meta-aluminic acid root；
The chloride ion may be from least one of following salt: sodium chloride, potassium chloride, calcium chloride, magnesium chloride, chlorination
Iron, frerrous chloride, copper chloride and stannous chloride；
The nitrate anion may be from least one of following salt: sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, nitric acid
Iron, ferrous nitrate, copper nitrate and cuprous nitrate；
The nitrite anions may be from least one of following salt: sodium nitrite, potassium nitrite, calcium nitrite, nitrous
Sour magnesium, nitrous acid iron, nitrous acid ferrous iron, cupric nitrite and nitrous acid are cuprous；
The MnO4 is from least one of following salt: potassium permanganate and sodium permanganate.
The anion of the multivalence is sulfate radical, inferior sulfate radical, over cure acid group, phosphate radical, orthophosphite, borate, lemon
At least one of lemon acid group, dioxygen root and Manganate ions；
The sulfate radical may be from least one of following salt: sodium sulphate, potassium sulfate, calcium sulfate, magnesium sulfate, sulfuric acid
Iron, ferrous sulfate, copper sulphate and cuprous sulfate；
The phosphate radical comes can be from least one of following salt: sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, phosphoric acid
Iron, ferrous phosphate, cupric phosphate, phosphoric acid is cuprous, tripolyphosphate and sodium glycero-phosphate；
The orthophosphite may be from least one of following salt: sodium phosphite, potassium phosphite, Arizona bacilli, phosphorous
Sour magnesium, phosphorous acid iron, phosphorous acid ferrous iron, phosphorous acid copper and phosphorous acid are cuprous；
The borate may be from borax；
The citrate may be from least one of following salt: sodium citrate, potassium citrate, calcium citrate, lemon
Sour magnesium, ironic citrate, ferrous citrate, copper citrate and citric acid are cuprous.
The anionic metal can be at least one of Pt (II), Pd (II) and Mo (VI)；
The radical initiator can be at least one of following initiator: benzoin ether derivative, aqueous acetophenone spread out
Biology, benzil analog derivative, Anthraquinones, thioxanthones, benzophenone, aqueous benzil analog derivative,
Water-soluble anthraquinone, aqueous thioxanthones, persulfate, azo it is one or more, wherein common initiator be 2- hydroxyl
Base -4- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 2- hydroxyl -1,2- diphenylethan, 2,4,6- (trimethylbenzoyl) two
Phenyl phosphine oxide, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, isopropyl thioxanthone anthraquinone,
4- benzoyl -4 '-methyl-diphenyl sulfide, 2- methyl -1- [4- methyl mercapto phenyl] -2- morpholinyl -1- acetone, 4- diformazan ammonia
Base-ethyl benzoate, benzophenone, benzil or 4,4 '-dimethylamino benzophenone, α-ketoglutaric acid, anthraquinone -2- sulphur
Acid sodium-salt, potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyrate hydrochloride (AIBA), two NSC 18620 oxazoline hydrochloride of azo
(AIBI) and azodiisobutyronitrile；
The aldehyde compound can be glutaraldehyde.
Invention further provides the chemical-physical/chemistry double-network hydrogel preparation method, including it is as follows
(1) or the step of (2):
(1)
1) the mixed of described polysaccharide or derivatives thereof, the polyethyleneglycol derivative 1 and the polyethyleneglycol derivative 2 is prepared
Close solution；
2) mixed solution is injected into mold, through cooling to obtain the final product；
(2)
1) mixed solution 1 of the described polysaccharide or derivatives thereof with the polyethyleneglycol derivative 1 is prepared；
2) mixed solution 2 of the described polysaccharide or derivatives thereof with the polyethyleneglycol derivative 2 is prepared；
3) through following step a) or b) up to the chemical-physical/chemistry double-network hydrogel:
A) mixed solution 1 and the mixed solution 2 are injected into mold, through cooling to obtain the final product；
B) mixed solution 1 and the mixed solution 2 are injected into mold, obtain the first chemical network water through cooling
Gel；The first chemical network hydrogel is soaked in the aqueous solution of the crosslinking agent to obtain the final product.
In above-mentioned preparation method, step (2) 1) in, in the mixed solution 1, the matter of described polysaccharide or derivatives thereof
Amount-volumetric concentration can be 0.01~1000mg/ml, concretely 10~20mg/ml, 10mg/ml or 20mg/ml, the poly- second
Quality-volumetric concentration of diol, derivatives 1 can be 0.01~1000mg/ml, concretely 80mg/ml, the polysaccharide or its spread out
The biological mass ratio with the polyethyleneglycol derivative 1 can be 1:0.01~100, concretely 1:4~8,1:4 or 1:8；
Step (2) 2) in, in the mixed solution 2, the quality-volumetric concentration of described polysaccharide or derivatives thereof can be 0.01
~1000mg/ml, concretely 10~20mg/ml, 10mg/ml or 20mg/ml, quality-body of the polyethyleneglycol derivative 2
Product concentration can be 0.01~1000mg/ml, concretely 80mg/ml, described polysaccharide or derivatives thereof spread out with the polyethylene glycol
The mass ratio of biology 2 can be 1:0.01~100, concretely 1:4~8,1:4 or 1:8.
Step (2) 3) b) in, the mass fraction of the aqueous solution of the crosslinking agent can be 0.0005%~90%, concretely
17%.
In above-mentioned preparation method, step (2) 3) a) in, the time of the cooling can be 1s~72h, concretely 1h~
5h, 1h, 2h, 3h, 4h or 5h；
Step (2) 3) b) in, the time of the cooling can be 1s~72h, concretely 1h~4h, 1h, 2h or 4h；It is described
The time of immersion can be 1min~72h, concretely 2h.
It is provided by the invention that there is the good high-strength chemistry of automatic recovery ability biocompatibility-physical/chemical dual network water
Gel has potential application in following field:
(1) Thermosensitive Material Used for Controlled Releasing of Medicine；
(2) tissue engineering bracket；
(3) medical sponge；
(4) medical inner matter；
(5) surface covering of medical inner matter.
Compared with prior art, the invention has the following beneficial effects:
(1) chemical-physical of the present invention/chemistry dual network gel preparation course is relatively easy, and the used time is short, and mechanical property is excellent
It is different.
(2) chemical-physical of the present invention/chemistry dual network gel can by being formed in situ, can in any grinding tool quilt
It is prepared into arbitrary shape.
(3) in chemical-physical of the present invention/chemistry dual network gel physical network have invertibity, self-reparability and resist it is tired
Lao Xing；After the load removal being applied on gel, physical network quickly can restore and recombinate, to restore its mechanicalness
Energy.
(4) chemical-physical of the present invention/chemistry dual network gel has very outstanding biocompatibility.
(5) chemical-physical of the present invention/chemistry dual network gel is capable of the growth of sertoli cell.
Detailed description of the invention
Fig. 1 is picture of the double-network hydrogel of the preparation of the embodiment of the present invention 1 in glass all one's effort by pressure.
Fig. 2 is that the double-network hydrogel of preparation of the embodiment of the present invention can be prepared into picture of various shapes.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1,
(1) it weighs high-intensitive agarose 200mg to be dissolved in 10mLPBS buffer solution, is cooled to 50 after being heated to 120 DEG C
DEG C, take 5mL that tetra- arm polyethylene glycol amino of 400mg is added thereto (as shown in Formula II, wherein n 56, R respectively1For ehter bond, R2
For amino) and tetra- arm polyethylene glycol succinimide ester of 400mg (as shown in Formula II, wherein n 56, R1For ester bond, R2For amber
Imide ester) obtain mixed solution 1 and mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, then
In implantation glass mold, 3 hours to be cooled arrive room temperature, obtain chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 28MPa, compressed shape variability is
97% or more.
After gel compression manufactured in the present embodiment, it can restore to former compressive strength, such as Fig. 1 within 2 hours in the case where being heated to 100 DEG C
For the shown double-network hydrogel that will be obtained the case where glass all one's effort is by pressure, gel was restored immediately to it originally after cancelling glass
Height.
Embodiment 2,
It weighs conventional agarose 200mg to be dissolved in 10mLPBS buffer solution, 50 DEG C is cooled to after being heated to 100 DEG C, respectively
Take 5mL that tetra- arm polyethylene glycol alkynyl of 400mg is added thereto (as shown in Formula II, wherein n 56, R1For ehter bond, R2For alkynyl)
With tetra- arm carboxyl nitrine of 400mg (as shown in Formula II, wherein n 56, R1For ehter bond, R2For nitrine) it obtains mixed solution 1 and mixes
Close solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then injected into mold, 2 hours to be cooled arrive room
Temperature obtains chemical-physical double-network hydrogel.
Using the different available hydrogels of different shapes of mold, as shown in Fig. 2, can prepare clover shape and
The hydrogel of snowflake shape.
Embodiment 3,
It weighs low melting-point agarose 200mg to be dissolved in 10mLPBS buffer solution, 50 DEG C is cooled to after being heated to 80 DEG C, point
Do not take 5mL that tetra- arm polyethylene glycol sulfydryl of 400mg is added thereto (as shown in Formula II, wherein n 56, R1For ehter bond, R2For mercapto
Base) and tetra- arm polyethylene glycol succinimide ester of 400mg (as shown in Formula II, wherein n 56, R1For ester bond, R2For succinyl Asia
Amine ester) obtain mixed solution 1 and mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then injected into
In mold, 4 hours to be cooled arrive room temperature, obtain chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 38MPa, compressed shape variability is
98% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 60 DEG C.
Embodiment 4,
It weighs high-intensitive agarose 200mg to be dissolved in 10mLPBS buffer solution, 50 DEG C is cooled to after being heated to 120 DEG C, point
Do not take 5mL that six arm polyethylene glycol sulfydryl of 400mg is added thereto (as shown in formula III, wherein n 43, R1For ehter bond, R2For mercapto
Base) and six arm polyethylene glycol succinimide ester of 400mg (as shown in formula III, wherein n 43, R1For ehter bond, R2For succinyl
Imines ester) obtain mixed solution 1 and mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then infused
Enter in mold, 1 hour to be cooled arrives room temperature, obtains chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 43MPa, compressed shape variability is
98% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 100 DEG C.
Embodiment 5,
It weighs conventional agarose 200mg to be dissolved in 10mL PBS buffer solution, 50 DEG C is cooled to after being heated to 100 DEG C, point
Do not take 5mL that six arm polyethylene glycol alkynyl of 400mg is added thereto (as shown in formula III, wherein n 23, R1For ester bond, R2For alkynes
Base) and six arm carboxyl nitrine of 400mg (as shown in formula III, wherein n 23, R1For ehter bond, R2For nitrine) obtain mixed solution 1
With mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then injected into mold, 2 hours to be cooled
To room temperature, chemical-physical double-network hydrogel is obtained.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 45MPa, compressed shape variability is
99% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 80 DEG C.
Embodiment 6,
It weighs low melting-point agarose 200mg to be dissolved in 10mL PBS buffer solution, 50 DEG C is cooled to after being heated to 80 DEG C, point
Do not take 5mL that six arm polyethylene glycol sulfydryl of 400mg is added thereto (as shown in formula III, wherein n 23, R1For ehter bond, R2For mercapto
Base) and six arm polyethylene glycol succinimide ester of 400mg (as shown in formula III, wherein n 23, R1For ester bond, R2For succinyl
Imines ester) obtain mixed solution 1 and mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then infused
Enter in mold, 2 hours to be cooled arrive room temperature, obtain chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 56MPa, compressed shape variability is
96% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 60 DEG C.
Embodiment 7,
It weighs high-intensitive agarose 200mg to be dissolved in 10mL PBS buffer solution, 50 DEG C is cooled to after being heated to 120 DEG C,
Take 5mL that eight arm polyethylene glycol sulfydryl of 400mg is added thereto (as shown in formula IV, wherein n 45, R respectively1For ehter bond, R2For mercapto
Base) and eight arm polyethylene glycol succinimide ester of 400mg (as shown in formula IV, wherein n 45, R1For amido bond, R2For succinyl
Imines ester) obtain mixed solution 1 and mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then infused
Enter in mold, 5 hours to be cooled arrive room temperature, obtain chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 43MPa, compressed shape variability is
98% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 100 DEG C.
Embodiment 8,
It weighs conventional agarose 200mg to be dissolved in 10mL PBS buffer solution, 50 DEG C is cooled to after being heated to 100 DEG C, point
Do not take 5mL that eight arm polyethylene glycol alkynyl of 400mg is added thereto (as shown in formula IV, wherein n 21, R1For ehter bond, R2For alkynes
Base) and eight arm carboxyl nitrine of 400mg (as shown in formula IV, wherein n 21, R1For ehter bond, R2For nitrine) obtain 1 He of mixed solution
Mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then injected into mold, 5 hours to be cooled arrive
Room temperature obtains chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 35MPa, compressed shape variability is
99% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 80 DEG C.
Embodiment 9,
It weighs low melting-point agarose 200mg to be dissolved in 10mL PBS buffer solution, 50 DEG C is cooled to after being heated to 80 DEG C, point
Do not take 5mL that eight arm polyethylene glycol sulfydryl of 400mg is added thereto (as shown in formula IV, wherein n 21, R1For ehter bond, R2For mercapto
Base) and eight arm polyethylene glycol succinimide ester of 400mg (as shown in formula IV, wherein n 21, R1For carbonic acid ester bond, R2For amber
Imide ester) obtain mixed solution 1 and mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, then
It injects in mold, 4 hours to be cooled arrive room temperature, obtain chemical-physical double-network hydrogel.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 46MPa, compressed shape variability is
97% or more.After gel compression, it can restore to former compressive strength within 2 hours in the case where being heated to 60 DEG C.
Embodiment 10,
(1) it weighs high-strength alginic acid sodium 100mg to be dissolved in 10mLPBS buffer solution, takes 5mL to be added thereto respectively
Tetra- arm polyethylene glycol sulfydryl of 400mg is (as shown in Formula II, wherein n 21, R1For ehter bond, R2For sulfydryl) and the poly- second of tetra- arm of 400mg
Glycol succinimide ester is (as shown in Formula II, wherein n 21, R1For ester bond, R2For succinimide ester) obtain mixed solution 1
With mixed solution 2；A kind of mixed solution is drawn with one of double syringe respectively, is then injected into mold, 4 hours to be cooled
To room temperature, the first chemical network hydrogel is obtained.
(2) then 20g calcium chloride is dissolved in the water of 100mL, is configured to cross-linking agent solution.By the first chemical network water
For soak 2 hours in calcium chloride solution, gel is opaque chemical-physical double-network hydrogel by transparent transition.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 53MPa, compressed shape variability is
98% or more.After gel compression, placing can restore to former tensile strength for 2 hours, and place after complete fatigue 6 hours can for gel
Restore shape and mechanical strength completely.
Embodiment 11,
(1) it weighs sodium alginate 100mg to be dissolved in 10mL PBS buffer solution, takes 5mL that 400mg six is added thereto respectively
Arm polyethylene glycol alkynyl is (as shown in formula III, wherein n 21, R1For ehter bond, R2For alkynyl) and six arm polyethylene glycol of 400mg it is folded
Nitrogen is (as shown in formula III, wherein n 21, R1For ehter bond, R2For nitrine) obtain mixed solution 1 and mixed solution 2；Respectively with double
One of pipe syringe draws a kind of mixed solution, is then injected into mold, and 2 hours to be cooled arrive room temperature, obtains the first chemistry
Network aqueous gel.
(2) then 20g calcium chloride is dissolved in the water of 100mL, is configured to cross-linking agent solution.By the first chemical network water
For soak 2 hours in calcium chloride solution, gel is opaque chemical-physical double-network hydrogel by transparent transition.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 65MPa, compressed shape variability is
99% or more.After gel compression, placing can restore to former tensile strength for 5 hours, and gel is placed 10 hours after complete fatigue
It can restore shape and mechanical strength completely.
Embodiment 12,
(1) it weighs sodium alginate 100mg to be dissolved in 10mLPBS buffer solution, takes 5mL that 400mg eight is added thereto respectively
Arm polyethylene glycol sulfydryl is (as shown in formula IV, wherein n 21, R1For ehter bond, R2For sulfydryl) and eight arm polyethylene glycol amber of 400mg
Imide ester is (as shown in formula IV, wherein n 21, R1For ester bond, R2For succinimide ester) it obtains mixed solution 1 and mixes molten
Liquid 2；A kind of mixed solution is drawn with one of double syringe respectively, is then injected into mold, 1 hour to be cooled arrives room temperature,
Obtain the first chemical network hydrogel.
(2) then 20g calcium chloride is dissolved in the water of 100mL, is configured to cross-linking agent solution.By the first chemical network water
For soak 2 hours in calcium chloride solution, gel is opaque chemical-physical double-network hydrogel by transparent transition.
Obtained chemical-physical double-network hydrogel is tested, compressive strength 46MPa, compressed shape variability is
98% or more.After gel compression, placing can restore to former tensile strength for 1 hour, and place after complete fatigue 6 hours can for gel
Restore shape and mechanical strength completely.
Embodiment 13,
(1) it weighs chitosan 100mg to be dissolved in 10mLPBS buffer solution, takes 5mL that eight arm of 400mg is added thereto respectively
Polyethylene glycol alkynyl is (as shown in formula IV, wherein n 21, R1For ehter bond, R2For alkynyl) and eight arm polyethylene glycol nitrine of 400mg
(as shown in formula IV, wherein n 21, R1For ester bond, R2For nitrine) obtain mixed solution 1 and mixed solution 2；Respectively with two-tube note
One of emitter draws a kind of mixed solution, is then injected into mold, and 1 hour to be cooled arrives room temperature, obtains the first chemical network
Hydrogel.
(2) then 20g glutaraldehyde is dissolved in the water of 100mL, is configured to cross-linking agent solution.By the first chemical network water
For soak 2 hours in glutaraldehyde solution, gel is opaque chemistry-chemistry double-network hydrogel by transparent transition.
Obtained chemistry-chemistry double-network hydrogel is tested, compressive strength 66MPa, compressed shape variability is
98% or more.After gel compression, placing can restore to former tensile strength for 2 hours, and place after complete fatigue 4 hours can for gel
Restore shape and mechanical strength completely.
Claims (6)
1. a kind of chemical-physical/chemistry double-network hydrogel, it is characterised in that: the chemical-physical/chemistry dual network water-setting
Glue is formed with the second physical/chemical network through interaction of hydrogen bond by the first chemical network；
First chemical network is formed by polyethyleneglycol derivative 1 and polyethyleneglycol derivative 2 through chemical reaction；
The second physical/chemical network be it is following 1) or 2):
1) by the crosslinked formation of polysaccharide or derivatives thereof；
2) it is interacted and is formed with crosslinking agent by polysaccharide or derivatives thereof；
2) in, the interaction is electrostatic interaction, crystallization, molecule aggtegation, ionization, hydrogen bond action or chain
Winding effect；
The crosslinking agent is at least one of alkali, the anion of unit price, the anion of multivalence and anionic metal；
Described polysaccharide or derivatives thereof is agar, agarose, sodium alginate, cellulose, starch, hyaluronic acid or their derivative
Object；
The polyethyleneglycol derivative 1 and the polyethyleneglycol derivative 2 are any in Formula II, formula III and formula IV:
In various, n is the number between 2 ~ 10000；
R1For ehter bond, acetyl group, ester bond, ammonia ester bond, amido bond or carbon atom number be 1 ~ 30 straight-chain, branched or cricoid
Alkylidene；
R2For amino, carboxyl, succinimide ester, aldehyde radical, sulfydryl, alkenyl, alkynyl, acrylate-based, acrylamido, nitrine
It is any in group, epoxy group, maleic amide group, catechol group, phenolic hydroxyl group, cyclodextrin, adamantane and azobenzene.
2. chemical-physical according to claim 1/chemistry double-network hydrogel, it is characterised in that: the alkali is organic base
Or inorganic base；
The anion of the unit price be chloride ion, fluorine ion, bromide ion, iodide ion, bicarbonate radical, bisulfite, nitrate anion,
At least one of nitrite anions, sulphur hydrogen radical, MnO4, hypochlorite, chlorate anions, metaphosphoric acid radical and meta-aluminic acid root；
The anion of the multivalence is sulfate radical, inferior sulfate radical, over cure acid group, phosphate radical, orthophosphite, borate, citric acid
At least one of root, dioxygen root and Manganate ions；
At least one of the anionic metal is Pt(II), Pd(II) and Mo(VI).
3. chemical-physical as claimed in claim 1 or 2/chemistry double-network hydrogel preparation method, including following (1) or (2)
Step:
(1)
1) it is molten that described polysaccharide or derivatives thereof, the polyethyleneglycol derivative 1 and the mixing of the polyethyleneglycol derivative 2 are prepared
Liquid；
2) mixed solution is injected into mold, through cooling to obtain the final product；
(2)
1) mixed solution 1 of the described polysaccharide or derivatives thereof with the polyethyleneglycol derivative 1 is prepared；
2) mixed solution 2 of the described polysaccharide or derivatives thereof with the polyethyleneglycol derivative 2 is prepared；
3) through following step a) or b) up to the chemical-physical/chemistry double-network hydrogel:
A) mixed solution 1 and the mixed solution 2 are injected into mold, through cooling to obtain the final product；
B) mixed solution 1 and the mixed solution 2 are injected into mold, obtain the first chemical network water-setting through cooling
Glue；The first chemical network hydrogel is soaked in the aqueous solution of the crosslinking agent to obtain the final product.
4. preparation method according to claim 3, it is characterised in that: step (2) 1) in, it is described in the mixed solution 1
Quality-volumetric concentration of polysaccharide or derivatives thereof is 0.01 ~ 1000mg/ml, quality-volume of the polyethyleneglycol derivative 1
Concentration is 0.01 ~ 1000mg/ml, the mass ratio of described polysaccharide or derivatives thereof and the polyethyleneglycol derivative 1 be 1:0.01 ~
100；
Step (2) 2) in, in the mixed solution 2, the quality-volumetric concentration of described polysaccharide or derivatives thereof is 0.01 ~
1000mg/ml, quality-volumetric concentration of the polyethyleneglycol derivative 2 are 0.01 ~ 1000mg/ml, the polysaccharide or its derivative
The mass ratio of object and the polyethyleneglycol derivative 2 is 1:0.01 ~ 100；
Step (2) 3) b) in, the mass fraction of the aqueous solution of the crosslinking agent is 0.0005% ~ 90%.
5. preparation method according to claim 3 or 4, it is characterised in that: step (2) 3) a) in, the time of the cooling
For 1s~72h；
Step (2) 3) b) in, the time of the cooling is 1s~72h；The time of the immersion is 1min~72h.
6. chemical-physical as claimed in claim 1 or 2/chemistry double-network hydrogel is preparing Thermosensitive Material Used for Controlled Releasing of Medicine, organizational project branch
Frame, medical sponge, medical inner matter or medical inner matter surface covering in application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610994581.4A CN106519264B (en) | 2016-11-10 | 2016-11-10 | Double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610994581.4A CN106519264B (en) | 2016-11-10 | 2016-11-10 | Double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106519264A CN106519264A (en) | 2017-03-22 |
| CN106519264B true CN106519264B (en) | 2019-02-26 |
Family
ID=58350853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610994581.4A Active CN106519264B (en) | 2016-11-10 | 2016-11-10 | Double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106519264B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864494B (en) * | 2017-05-09 | 2021-03-05 | 中国科学院大学 | Dynamic cross-linked double-network hydrogel and preparation method and application thereof |
| CN109575315B (en) * | 2017-09-29 | 2021-12-24 | 中国科学院大学 | PVA supramolecular hydrogel and preparation method and application thereof |
| CN107596438B (en) * | 2017-10-26 | 2018-09-07 | 山东大学 | A kind of natural polysaccharide self-healing hydrogel of injectable and the preparation method and application thereof |
| CN108159482A (en) * | 2018-01-02 | 2018-06-15 | 上海其胜生物制剂有限公司 | A kind of injectable natural hydrogel system with temperature-sensing property and high bioadhesion and preparation method thereof |
| CN108546333A (en) * | 2018-03-26 | 2018-09-18 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation of high-mechanical property dual network composite hydrogel |
| CN108409997B (en) * | 2018-03-29 | 2021-02-19 | 武汉大学苏州研究院 | Preparation method of ultrahigh-strength anisotropic hydrogel containing cellulose nanowhiskers |
| CN112957518B (en) * | 2018-08-20 | 2022-10-25 | 稳得希林(杭州)生物科技有限公司 | Polysaccharide-based tissue adhesive medical adhesive and application thereof |
| CN109481732B (en) * | 2018-12-29 | 2021-07-27 | 中国科学院理化技术研究所 | 3D cell printing material based on PEG chitosan-gelatin system and application thereof |
| CN110240712B (en) * | 2019-05-09 | 2021-04-23 | 大连理工大学 | High-tensile, high-viscosity and self-healing double-network hydrogel for tissue adhesion and preparation method and application thereof |
| CN110680959B (en) * | 2019-10-31 | 2021-12-03 | 江苏地韵医疗科技有限公司 | Hydrogel for repairing multiple cross-linked meniscus and preparation method thereof |
| CN111388748B (en) * | 2020-03-03 | 2021-08-06 | 东华大学 | Antibacterial and hemostatic multifunctional composite hydrogel dressing and preparation method thereof |
| CN112624071A (en) * | 2021-01-17 | 2021-04-09 | 黔南民族师范学院 | Preparation method of ferrous phosphite |
| CN115515652A (en) | 2021-04-14 | 2022-12-23 | 北京博辉瑞进生物科技有限公司 | Medical hydrogel and preparation method and application thereof |
| CN113289051B (en) * | 2021-05-19 | 2022-06-17 | 南方科技大学 | PEG powder capable of being rapidly crosslinked and degraded and application thereof |
| CN114203454B (en) * | 2021-11-26 | 2022-07-29 | 广东省科学院化工研究所 | Gel electrolyte thermal charging/electric charging super capacitor and preparation method thereof |
| CN115998952A (en) * | 2023-01-30 | 2023-04-25 | 江西博恩锐尔生物科技有限公司 | Gel material for promoting tissue regeneration and repair and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911381A (en) * | 2012-11-12 | 2013-02-06 | 天津工业大学 | Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof |
| CN103739861A (en) * | 2014-01-02 | 2014-04-23 | 河南理工大学 | Preparation method of high-strength hydrogel |
| CN104610495A (en) * | 2015-02-05 | 2015-05-13 | 中国科学院兰州化学物理研究所 | Preparation method of bi-crosslinked hydrogel |
| CN105461945A (en) * | 2015-12-29 | 2016-04-06 | 华南理工大学 | Ion-covalent double-network hydrogel and preparation method thereof |
| CN106009003A (en) * | 2016-07-11 | 2016-10-12 | 吉林大学 | Injectable self-repairing hydrogel based on polysaccharides, preparation method and application of hydrogel to biological tissue engineering |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011609A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-strength chemical-physical double-network hydrogel with automatic recovery ability and preparation method and application |
-
2016
- 2016-11-10 CN CN201610994581.4A patent/CN106519264B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911381A (en) * | 2012-11-12 | 2013-02-06 | 天津工业大学 | Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof |
| CN103739861A (en) * | 2014-01-02 | 2014-04-23 | 河南理工大学 | Preparation method of high-strength hydrogel |
| CN104610495A (en) * | 2015-02-05 | 2015-05-13 | 中国科学院兰州化学物理研究所 | Preparation method of bi-crosslinked hydrogel |
| CN105461945A (en) * | 2015-12-29 | 2016-04-06 | 华南理工大学 | Ion-covalent double-network hydrogel and preparation method thereof |
| CN106009003A (en) * | 2016-07-11 | 2016-10-12 | 吉林大学 | Injectable self-repairing hydrogel based on polysaccharides, preparation method and application of hydrogel to biological tissue engineering |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis and properties of hemostatic and bacteria-responsive in situ hydrogels for emergency treatment in critical situations";Yazhong Bu等;《ACS Appl. Mater. Interfaces》;20160509;第8卷(第20期);第12674-12683页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106519264A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106519264B (en) | Double-network hydrogel and the preparation method and application thereof based on PEG and polysaccharide | |
| CN107011609A (en) | A kind of high-strength chemical-physical double-network hydrogel with automatic recovery ability and preparation method and application | |
| Su et al. | A self-healing and highly stretchable polyelectrolyte hydrogel via cooperative hydrogen bonding as a superabsorbent polymer | |
| CN105504166A (en) | Sodium alginate-acrylamide composite aquagel, and preparation method and application thereof | |
| CN107254056B (en) | Self-healing polyvinyl alcohol-alginate double-network gel and preparation method thereof | |
| CN108559108B (en) | Preparation method of three-dimensional interpenetrating network hydrogel with pH response | |
| CN107603106A (en) | A kind of preparation method of three network combined hydrogel of acrylamide polyvinyl alcohol acrylic acid calcium chloride | |
| CN106866998B (en) | A kind of chitosan quaternary ammonium salt/carboxymethyl cellulose superabsorbent hydrogel and its preparation method and application | |
| CN103013014A (en) | Super-strong hydrogel with plurality of networks and preparation method thereof | |
| CN107812540B (en) | Non-recovery natural polysaccharide hydrogel-based photocatalyst pre-radiation synthesis method | |
| Zhang et al. | Joint double-network hydrogels with excellent mechanical performance | |
| CN110204746A (en) | A kind of preparation method of cross-linking sodium hyaluronate gel | |
| CN104845382A (en) | Silk protein/cellulose derivative blending hydrogel and preparation method thereof | |
| Sharma et al. | γ-radiation induced synthesis of antibacterial silver nanocomposite scaffolds derived from natural gum Boswellia serrata | |
| CN111253591A (en) | Double-crosslinked hyaluronic acid hydrogel, and preparation method and application thereof | |
| Taaca et al. | Current trends in biomedical hydrogels: From traditional crosslinking to plasma-assisted synthesis | |
| Hu et al. | Recent Advances in Polysaccharide‐Based Physical Hydrogels and Their Potential Applications for Biomedical and Wastewater Treatment | |
| CN106267366A (en) | A kind of method that high-strength and high ductility polyion hydrogel scaffold is prepared in the 3D of utilization printing | |
| CN109294001A (en) | It is a kind of uniformly in crossslinked sodium alginate film and preparation method thereof | |
| CN102924725B (en) | Polyamino acid/chitosan composite material and preparation method thereof | |
| CN112625183A (en) | High-strength photo-crosslinking antibacterial hydrogel and preparation method thereof | |
| CN106243323B (en) | A kind of saline-alkali tolerant height inhales the preparation method of the carboxymethyl cellulose-based sustained-release micro-spheres of fertilizer | |
| CN107325301A (en) | A kind of high intensity γ polyglutamic acid hydrogels | |
| CN107056983A (en) | Prepare orthogonal regulation and control mechanical performance and medicine-releasing performance double-network hydrogel method | |
| CN107936198B (en) | Medical gel eye mask material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211118 Address after: 361006 unit 03, 8 / F, building D, Xiamen international shipping center, No. 97, Xiangyu Road, Xiamen area (Free Trade Zone), China (Fujian) pilot Free Trade Zone, Huli District, Xiamen City, Fujian Province Patentee after: Xiamen fuyuantang Investment Management Co.,Ltd. Address before: 100190 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee before: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221123 Address after: 518110 A1702, Building 1, Yinxing Zhijie Phase II, No. 1301-76, Sightseeing Road, Xinlan Community, Guanlan Street, Longhua District, Shenzhen, Guangdong Patentee after: Shenzhen Ningju Biological New Material Technology Co.,Ltd. Address before: 361006 unit 03, 8 / F, building D, Xiamen international shipping center, No. 97, Xiangyu Road, Xiamen area (Free Trade Zone), China (Fujian) pilot Free Trade Zone, Huli District, Xiamen City, Fujian Province Patentee before: Xiamen fuyuantang Investment Management Co.,Ltd. |
|
| TR01 | Transfer of patent right |